Patent Publication Number: US-2021163384-A1

Title: Compositions and Methods for Reducing Enones to Saturated Alcohols

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     The present application claims the benefit of priority under 35 U.S.C. § 119(e) to U.S. Provisional patent Application No. 62/942,673, filed Dec. 2, 2019, the contents of which are incorporated herein by reference their entirety. 
    
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT 
     This invention was made with government support under DA036151 awarded by National Institutes of Health and under 1339637 awarded by National Science Foundation. The government has certain rights in the invention. 
    
    
     BACKGROUND OF THE INVENTION 
     C-glycosides have attracted considerable interest as mimics of conventional bioactive 0-glycosides. C-glycosides can be synthesized via condensation of pentane-2,4-dione with unprotected carbohydrates in alkaline aqueous media. The method is in accordance with green chemistry principles and provides access to bio-based, renewable building blocks. The substitution of the 0-glycosidic bond for a carbon-carbon linkage makes these molecules more resistant to acid and enzymatic degradation, thus rendering these compounds of great interest for applications such as anti-tumor agents, antidiabetics, antibiotics, anti-aging molecules, surfactants, and anti-inflammatory compounds. For example, reduction of the Lubineau C-glycoside 1 provided PRO-XYLANE™, a cosmetic ingredient, that stimulates sulfated glycosaminoglycans (GAGs) synthesis, and was launched on the market in 2006 as an active ingredient in skin anti-aging products (Cavezza, et al., 2009, Bioorg. Med. Chem. Lett. 19:845-849). 
     Aldol reactions and condensations are particularly important for the generation of novel C—C bonds, and will become even more relevant as chemists further embrace sustainability measures, since these reactions can adhere to many green chemistry concepts. Moreover, biomass-derived, renewable molecules are generally more oxidized and oxygenated than petroleum-based molecules. Thus, reactions that take advantage of the higher degree of oxygen groups, such as aldol reactions, will become even more important as the chemical industry shifts its focus towards sustainability. In fact, aldol reactions have already been extensively utilized on carbohydrate compounds and optimized for the syntheses of enone C-glycosides. For example, cyclic and linear C-glycosides can be synthesized using aldol condensation reactions. Recently, a greener and more efficient aldol methodology was developed to synthesize C-glycosidic enones from the Lubineau ketone using L-proline and magnesium oxide or hydrotalcite as a solid base catalyst. The method was used to generate a library of enone analogues, which demonstrated the utility and robustness of the novel methodology (de Winter, et al., 2018, ACS Sustainable Chemistry &amp; Engineering, DOI: 10.1021/acssuschemeng.8b02535; de Winter, et al., 2018, ACS Sus. Chem. &amp; Eng. 6:7810-7817). 
     Enones, however, can be bioactive due to their electrophilicity, especially at the β-carbon, enabling Michael acceptor reactivity. Michael acceptors are known toxicophores and can elicit interactions with various nucleophiles in cells without prior metabolic activation. For inherent safe design of molecular products, without unintended consequences, the development of selective, economical, and efficient chemical reductions of enones becomes important. Many methods for enone reductions have been developed, but most rely on the use of noble metal catalysts. Primarily, full reductions of enones are still performed in two sequential reactions: the double bond is first reduced (typically using ruthenium (Ru), palladium (Pd), or platinum (Pt), plus hydrogen (H 2 )) and then, after isolation of the intermediate ketone, the carbonyl is reduced using sodium borohydride (NaBH 4 ). 
     Thus, there is a need in the art for a practical, economical, and sustainable direct reduction of enones to the corresponding saturated alcohols. Such reduction reaction should allow for scalable synthetic routes for bioactive and/or industrially important compounds. The present invention addresses this need. 
     BRIEF SUMMARY OF THE INVENTION 
     The present invention provides a method of reducing an α,β-unsaturated ketone to its corresponding saturated alcohol. In certain embodiments, the method comprises contacting the α,β-unsaturated ketone, a solvent, a copper-doped porous metal oxide, and an inorganic hydride, thus forming a reaction mixture. 
     In certain embodiments, the solvent comprises methanol or water. In certain embodiments, the reaction mixture is kept at a temperature ranging from 0° C. to about 100° C. In certain embodiments, the inorganic hydride is selected from the group consisting of sodium borohydride and lithium borohydride. In certain embodiments, the metal oxide comprises copper(II), magnesium(II), and aluminum (III). In certain embodiments, the reaction mixture does not comprise hydrogen gas. In certain embodiments, the reaction mixture further comprises hydrogen gas. In certain embodiments, the reaction is run for about 1 hour to about 24 hours. In certain embodiments, the concentration of the α,β-unsaturated ketone in the reaction mixture is about 0.01-0.1 M. In certain embodiments, the reaction mixture is passed through a flow through reactor. In certain embodiments, the reaction mixture is formed within a flow through reactor. 
     In certain embodiments, the ratio of [copper(II)+magnesium(II)] to aluminum(III) is about 1.5:1 to about 6:1. In certain embodiments, the ratio of copper(II) to magnesium (II) is about 1:9 to about 4:6. 
     In certain embodiments, the pressure of hydrogen gas used ranges from about 1 to 10 MPa. 
     In certain embodiments, the amount of inorganic hydride used corresponds to about 2 to about 100 hydride equivalents in terms of the α,β-unsaturated ketone. In certain embodiments, the amount of the metal oxide used corresponds to about 5 to about 500 mol % in terms of the α,β-unsaturated ketone. 
     In certain embodiments, the reaction mixture is quenched by acidification. In certain embodiments, the quenched reaction mixture is purified by a separation method that separates solid material from the product-containing solution. In certain embodiments, the solid material is extracted at least once with an alcohol. In certain embodiments, the at least one alcohol extract is combined with the product-containing solution. In certain embodiments, the saturated alcohol is isolated from the product-containing solution. 
     In certain embodiments, the 3-position of the α,β-unsaturated ketone is substituted with an optionally substituted aliphatic or optionally substituted aromatic group. In certain embodiments, the 1-position of the α,β-unsaturated ketone is substitute with an optionally substituted (glycosyl)methyl group. 
     The present invention further provides a method of reducing an α,β-unsaturated ketone to its corresponding saturated ketone. In certain embodiments, the method comprises contacting the α,β-unsaturated ketone, a solvent, a copper-doped porous metal oxide, and hydrogen gas to form a reaction mixture. 
     In certain embodiments, the reaction mixture further comprises a Lewis acid. In certain embodiments, the solvent comprises methanol or water. In certain embodiments, the reaction mixture is kept at a temperature ranging from 0° C. to about 100° C. In certain embodiments, the metal oxide comprises copper(II), magnesium(II), and aluminum (III). In certain embodiments, the pressure of hydrogen gas used ranges from about 1 to 10 MPa. In certain embodiments, the reaction is run for about 1 hour to about 24 hours. In certain embodiments, the concentration of the α,β-unsaturated ketone in the reaction mixture is about 0.01-0.1 M. In certain embodiments, the metal oxide used corresponds to about 1 to about 100 mol % in terms of the α,β-unsaturated ketone. In certain embodiments, the reaction mixture is passed through a flow through reactor. In certain embodiments, the reaction mixture is formed within a flow through reactor. 
     In certain embodiments, the ratio of [copper(II)+magnesium(II)] to aluminum(III) is about 1.5:1 to about 6:1. In certain embodiments, the ratio of copper(II) to magnesium (II) is about 1:9 to about 4:6. 
     In certain embodiments, the reaction mixture is quenched by acidification. In certain embodiments, the quenched reaction mixture is purified by a separation method that separates solid material from the product-containing solution. In certain embodiments, the solid material is extracted at least once with an alcohol. In certain embodiments, the at least one alcohol extract is combined with the product-containing solution. In certain embodiments, the saturated ketone is isolated from the product-containing solution. 
     In certain embodiments, the 3-position of the α,β-unsaturated ketone is substituted with an optionally substituted aliphatic or an optionally substituted aromatic. In certain embodiments, the 1-position of the α,β-unsaturated ketone is substituted with an optionally substituted (glycosyl)methyl group. 
     In certain embodiments, the α,β-unsaturated ketone is an optionally substituted 2-propen-1-one and its corresponding saturated alcohol is an optionally substituted propan-1-ol. In certain embodiments, the α,β-unsaturated ketone is an optionally substituted 2-propen-1-one and its corresponding saturated ketone is an optionally substituted propan-1-one. 
    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
       For the purpose of illustrating the invention, depicted in the drawings are certain embodiments of the invention. However, the invention is not limited to the precise arrangements and instrumentalities of the embodiments depicted in the drawings. 
         FIG. 1A  illustrated previous work enabling syntheses of C-glycosides (Rodrigues, et al., 2000, Chem. Commun. 0:2049-2050; Cavezza &amp; Dalko, WO2010063948A2, 2010; Ramakrishna, et al., 2014, ACS Med. Chem. Lett. 5:878-883). 
         FIG. 1B  illustrates an illustrative full Cu-PMO catalyzed reduction of glycoside enones according to certain embodiments of the invention. 
         FIG. 2  illustrates non-limiting examples of the copper-catalyzed full reduction of C-glycosidic aromatic enones. All NMR yields are calculated from NMR spectroscopy of the crude reaction mixture using an internal standard. Isolated yields were calculated after weighing and NMR verification of the absence of boron salts. All reactions showed full conversion of the starting material using NMR quantitation. *The reaction also furnished 36% unsaturated alcohol 4f. **The reaction also furnished 15% of unsaturated alcohol 4g. 
         FIG. 3  illustrates the copper-catalyzed full reduction of the C-glycosidic aromatic enones 2f and 2g to the corresponding, saturated alcohols. All reactions showed full conversion of starting materials using NMR quantitation. Isolated yields were calculated using the masses of product mixtures after NMR verification of the absence of boron salts. All reactions showed full conversion of the starting material using NMR quantitation. *The reaction also furnished 36% unsaturated alcohol 4f. 
         FIG. 4  illustrates non-limiting examples of the copper-catalyzed full reduction of C-glycosidic aliphatic enones. All yields are calculated from NMR spectroscopy of the crude reaction mixture using CHCl 3  as an internal standard. All reactions showed full conversion of the starting material using NMR quantitation. 
         FIG. 5  illustrates a XPRD spectrum of Cu-PMO catalyst. 
         FIG. 6  illustrates a XRPD spectrum of the HTC catalyst. 
         FIG. 7  illustrates initial structures of the two diastereomers used for the conformational search with the numbering of the atoms; white—hydrogen, red—oxygen, gray—carbon. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The invention relates, in certain aspects, to synthetic routes that allow for direct reduction of enones to the corresponding saturated alcohols. Such reactions are compatible with a wide range of functional groups, and expand the repertoire of existing green chemistry methodology. In certain embodiments, the reactions are run in aqueous solvent. In certain embodiments, a reaction mixture contemplated within the invention is passed through a flow through reactor. In other embodiments, a reaction mixture contemplated within the invention is formed within a flow-through reactor. In certain embodiments, the catalyst is immobilized and/or coated on a solid support. In other embodiments, the immobilized and/or coated-on catalyst and the reaction mixture are contacted in a packed bed reactor. In yet other embodiments, the catalyst is immobilized and/or coated on a reactor surface. In yet other embodiments, the reaction mixture is contacted with the catalyst immobilized and/or coated on a reactor surface. 
     Metal-hydrides, such as copper hydride, can be used for the 1,2- and 1,4-chemo- and enantio-selective reductions of enones (Lipshutz, 2002, in Modern Organocopper Chemistry, ed. N. Krause, Wiley-VCH Verlag GmbH, Weinheim, Germany, ch. 5, pp. 167-187; Deutsch, et al., 2008, Chem. Rev. 108:2916-2927; Lipshutz, 2014, in Copper-Catalyzed Asymmetric Synthesis, eds. A. Alexakis, N. Krause and S. Woodward, Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim, Germany, ch. 7, pp. 179-201). Further, a heterogeneous copper-doped porous metal oxide (Cu-PMO) catalyst can be employed in selective hydrogenations of alkenes, as well as hydrogenolysis and hydrogenation of aryl ketones (Petitjean, et al., 2016, Green Chem. 18:150-156). Porous metal oxides (PMOs) are derived from hydrotalcite-like precursors of formula M 2+   6 M 3+   2 CO 3 (OH) 16 .4H 2 O, which often possess high surface area, and are highly tunable by altering M 2+ :M 3+  ratio, and by including other metal dopants (Debecker, et al., 2009, Chem. Eur. J. 15:3920-3935). Cu-PMO is synthesized by co-precipitation of Cu 2+ , Mg 2+  and Al 3+  nitrate salts in basic aqueous media, with M 2+ :M 3+  kept at 3:1 and Cu composing 20 mol % of M 2+ . After calcination in air, Cu-PMO is obtained as an amorphous solid with metal ratios Cu 0.57 Mg 2.27 Al 1.00 . Cu-PMO has the advantages of being entirely composed of earth-abundant elements, inexpensive, and long-lasting on the shelf. The heterogeneous nature of Cu-PMO lessens the cost of product isolation and enables easy recyclability, thus reducing environmental and financial costs. 
     The present disclosure relates in part to the investigation and successful development of the Cu-PMO catalyzed reduction of aromatic and aliphatic C-glycosidic enones to the corresponding fully saturated alcohols ( FIG. 1B ). The present methodology combines several principles of green chemistry: the use of renewable C-glycosidic substrates, of water as a benign solvent, the minimization of derivatives by performing the reduction on non-protected glycosides, the use of catalysis, especially with the earth-abundant elements, and the lack of extensive purifications, which lowers the amount of generated waste. Further, the present methodology allows access to safer molecules with an easy-to-implement reduction of potentially toxic, reactive enone moieties. 
     Enones were prepared following the general procedure shown in  FIGS. 1A-1B . For example, enone 2a ( FIG. 1A , R=H) was prepared from Lubineau C-Glycoside 1 (R=H) and benzaldehyde, following a protocol that employs L-proline and a solid base catalyst (de Winter, et al., 2018, ACS Sus. Chem. &amp; Eng. 6:7810-7817). 
     The invention relates, in certain aspects, to synthetic routes that allow for the reduction of enones to the corresponding ketones. The use of Cu-PMO (11 mol %) and 4 MPa of hydrogen at 100° C., for 18 hours in methanol (0.01 M), provided very selective and quantitative conversion of the starting C-glycosidic enone to the corresponding ketone 5a (See Example 1, Part K, under “5. C-Glycosidic ketones 5a and 5d”). Similar reactivity was observed when methanol was replaced with water, while keeping all other conditions the same. This result represents a selective, conjugate reduction of an enone in water with a heterogeneous catalyst made of earth-abundant elements. In certain non-limiting embodiments, the reduction does not require an added base for catalyst stability or for turnover rate enhancement, or a ligand for hydride stabilization. 
     The invention relates, in certain aspects, to synthetic routes that allow for the reduction of enones to the corresponding saturated alcohols. In a non-limiting example, the methodology provides quantitative and clean conversion of enone 2a (R=H) to the desired product 3a ( FIG. 2 ). Stirring of enone 2a with Cu-PMO (11 mol %) and NaBH 4  (2 equivalents) at 100° C., for 5 hours, in H 2 O (0.05 M) provided the desired product 3a in quantitative yield ( FIG. 2 ). In another non-limiting example, stirring of enone 2a with Cu-PMO (11 mol %) and NaBH 4  (2 equivalents) at 100° C. under hydrogen pressure (4 MPa), for 1-2 hours, in methanol (0.05 M) provided the desired product 3a in quantitative yield. In yet another non-limiting example, stirring of enone 2a with Cu-PMO (11 mol %) and NaBH 4  (2 equivalents) at 100° C. under hydrogen pressure (4 MPa), for 2 hours, in water (0.05 M) provided the desired product 3a in quantitative yield. Yet other embodiments are reported in Table 1. 
     The desired products were easily isolated without the need for further purification after a simple work-up procedure. The crude reaction mixtures were acidified with Amberlite IR-120H +  resin, followed by removal of the catalyst and resin by filtration, and washing the filtered residue with methanol. Concentration of the filtrate by rotatory evaporation and drying under high vacuum provided the desired product (as a diastereomeric mixture) in high yield. The absence of boron salts was confirmed by  1 H and  11 B NMR analysis. If boron salts were present, the mixture was re-dissolved in methanol and evaporated in vacuo, and the process was repeated until the absence of boron salts was confirmed by NMR. The Smith and Goodman&#39;s methodology was used for assigning diastereomers using computational modelling of NMR chemical proton and carbon shifts (Smith &amp; Goodman, 2009, J. Org. Chem. 74:4597-4607). 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 One step Cu-catalyzed full reduction of C-Glycosidic enones* 
               
            
           
           
               
               
               
               
            
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                   
                 NMR 
                 NMR Yield 
                 NMR Yield 
                 NMR Yield 
               
               
                 Entry 
                 Cat. (mol %) 
                 Temp (° C.) 
                 H 2  (MPa) 
                 Time (h) 
                 Add. (Eq.) 
                 solvent (M) 
                 Conversion (%) 
                 3a (%) 
                 4a (%) 
                 58 (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 CuPMO (11) 
                 100 
                 4 
                 18 
                 NaBH 4  (2) 
                 MeOH (0.01) 
                 100 
                 &gt;95 
                 0 
                 0 
               
               
                 2 
                 CuPMO (11) 
                 100 
                 4 
                 18 
                 NaBH 4  (2) 
                 MeOH (0.05) 
                 100 
                 &gt;95 
                 0 
                 0 
               
               
                 3 
                 CuPMO (11) 
                 100 
                 4 
                 4 
                 NaBH 4  (2) 
                 MeOH (0.05) 
                 100 
                 &gt;95 
                 0 
                 0 
               
               
                 4 
                 CuPMO (11) 
                 100 
                 4 
                 2 
                 NaBH 4  (2) 
                 MeOH (0.05) 
                 100 
                 &gt;95 
                 0 
                 0 
               
               
                 5 
                 CuPMO (11) 
                 100 
                 4 
                 1 
                 NaBH 4  (2) 
                 MeOH (0,05) 
                 100 
                 92 
                 0 
                 0 
               
               
                 6 
                 CuPMO (11) 
                 100 
                 4 
                 2 
                 NaBH 4  (2) 
                 H 2 O (0.05) 
                 100 
                 &gt;95 
                 0 
                 0 
               
               
                 7 
                 CuPMO (11) 
                 100 
                 — 
                 5 
                 NaBH 4  (2) 
                 H 2 O (0.05) 
                 100 
                 &gt;95 
                 0 
                 0 
               
               
                   
               
               
                 *DMF or CHCl3 were used as internal standards for NMR quantitations 
               
            
           
         
       
     
     The scope of the method was evaluated using various aryl substituted C-glycosidic enones ( FIG. 2 ). The L-proline and solid base catalyst protocol was used to prepare the enone substrates by condensing xylose- or glucose-derived Lubineau ketones with substituted benzaldehydes. Trifluoromethyl-substituted 3f/3f′ and fluoro-substituted 3g/3g′ were obtained in moderate (63%) and high (87%) yields, respectively, along with the unsaturated (allylic) alcohols 4f and 4g ( FIG. 2 ). A two-fold increase in the catalyst loading resulted in full and selective conversion of the trifluoromethyl-substituted and fluoro-substrates to the fully reduced alcohols 3f/3f′ and 3g/3g′, respectively ( FIG. 3 ). 
     The reaction conditions are amenable to the reduction of aliphatic C-glycosidic enones ( FIG. 4 ). The aliphatic enones were fully and selectively reduced to the corresponding aliphatic alcohols 3i/3i′ and 3j/3j′ in high yields. Compound 2j is prone to UV-induced deconjugation, and is obtained from aldol condensation as a mixture with deconjugated isomer 2j′ in a 2:1 ratio of 2j:2j′ ( FIG. 4 ). The present methodology furnishes desired product 3j/3j′ in 70% yield whereas the alcohol 6j/6j′ is obtained in 30% yield. 
     Heterogeneous catalysts provide the advantage of facile recyclability, necessitating, in our case, solely a filtration for catalyst recovery after reaction. In certain embodiments, Cu-PMO can be recycled further without loss of activity or selectivity. In addition to the recycling of the catalyst, Amberlite IR-120 H +  can be regenerated and re-used after treatment with a mineral acid. 
     In certain embodiments, any of the reaction mixture contemplated herein is free of organic solvents. 
     The applicability of the method was tested on multigram scale. Reduction of 2e (8.1 g) provided 5.1 g of pure product 3e/3e′ (73% isolated yield) after short path filtration of the crude over silica. The optimized reaction conditions were robust without alterations to large, industrially relevant scales. 
     In summary, the present report relates to the successful development and optimization of a novel method for the reduction of α,β-unsaturated enones to the corresponding fully saturated alcohols. The method employs a heterogeneous copper catalyst in water and requires only resin-treatment for isolation of C-glycosidic alcohols as pure, diastereomeric mixtures. Furthermore, the process of the invention is a green alternative to the two-step, precious noble metal and stoichiometric methodologies typically utilized to achieve full enone reduction. 
     Compounds of the present teachings can be prepared in accordance with the procedures outlined herein, from commercially available starting materials, compounds known in the literature, or readily prepared intermediates, by employing standard synthetic methods and procedures known to those skilled in the art. Standard synthetic methods and procedures for the preparation of organic molecules and functional group transformations and manipulations can be readily obtained from the relevant scientific literature or from standard textbooks in the field. It should be contemplated that the invention includes each and every one of the synthetic schemes described and/or depicted herein. 
     Methods 
     The invention provides a method of reducing an α,β-unsaturated ketone (optionally substituted 2-propen-1-one) to the corresponding saturated alcohol (optionally substituted propan-1-ol). 
     In certain embodiments, the method comprises contacting the α,β-unsaturated ketone, a solvent, a copper-doped porous metal oxide, and an inorganic hydride, thus forming a reaction mixture. In other embodiments, the solvent comprises methanol. In yet other embodiments, the solvent comprises water. In yet other embodiments, the reaction mixture is free of organic solvents. In yet other embodiments, the reaction mixture is kept at a temperature ranging from 0° C. to about 100° C. 
     In certain embodiments, the inorganic hydride is selected from the group consisting of sodium borohydride and lithium borohydride. 
     In certain embodiments, the metal oxide comprises copper(II), magnesium(II), and aluminum (III). In yet other embodiments, the ratio of [copper(II)+magnesium(II)] to aluminum(III) is about 1.5:1 to about 6:1. In yet other embodiments, the ratio of [copper(II)+magnesium(II)] to aluminum(III) is about 3:1. In yet other embodiments, the ratio of copper(II) to magnesium (II) is about 1:9 to about 4:6. In yet other embodiments, the ratio of copper(II) to magnesium (II) is about 2:8. 
     In certain embodiments, the reaction mixture does not comprise hydrogen gas. In certain embodiments, the reaction mixture further comprises hydrogen gas. In other embodiments, the pressure of hydrogen gas used ranges from about 1 to 10 MPa. 
     In certain embodiments, the reaction is run for about 1 hour to about 24 hours. 
     In certain embodiments, the amount of inorganic hydride used corresponds to about 2 to about 100 hydride equivalents in terms of the α,β-unsaturated ketone. In certain embodiments, the amount of inorganic hydride used corresponds to about 2 to about 40 equivalents in terms of the α,β-unsaturated ketone. 
     In certain embodiments, the concentration of the α,β-unsaturated ketone in the reaction mixture is about 0.01-0.1 M. 
     In certain embodiments, the amount of metal oxides used corresponds to about 5 to about 100 mol % in terms of the α,β-unsaturated ketone. 
     In certain embodiments, the reaction mixture is free of organic solvents. In other embodiments, the reaction mixture comprises at least one organic solvent. 
     In certain embodiments, the reaction mixture is quenched by acidification. In other embodiments, the acidification comprises adding an acidic resin to the reaction mixture. In yet other embodiments, the resin comprises a weakly acidic or strongly acidic resin. In yet other embodiments, the quenched reaction mixture is purified by a separation method that separates solid material from the product-containing solution. In yet other embodiments, the separation method comprises decantation, filtration, and/or centrifugation. In yet other embodiments, the solid material is extracted at least once with an alcohol. In yet other embodiments, the alcohol comprises methanol or ethanol. In yet other embodiments, the at least one alcohol extract is combined with the product-containing solution. In yet other embodiments, the saturated alcohol is isolated from the product-containing solution. In yet other embodiments, the isolation of the saturated alcohol comprises extraction, evaporation, or concentration under vacuum. In yet other embodiments, any boron species is at least partially removed from the product mixture by treatment with borate-specific chelating resin before addition of an alcohol. 
     In certain embodiments, the desired product is isolated by any chromatographic method known in the art. 
     In certain embodiments, the substitution at the 3-position of the ketone is an optionally substituted aliphatic or optionally substituted aromatic group. In certain embodiments, the substitution at the 1-position of the ketone is an optionally substituted (glycosyl)methyl group. 
     The invention also provides a method of reducing an α,β-unsaturated ketone (optionally substituted 2-propen-1-one) to the corresponding saturated ketone (optionally substituted propan-1-one). 
     In certain embodiments, the method comprises contacting the α,β-unsaturated ketone compound, a solvent, a copper-doped porous metal oxide, and hydrogen gas to form a reaction mixture. 
     In certain embodiments, the reaction mixture further comprises a Lewis acid. In other embodiments, the Lewis acid is at least one salt selected from the group consisting of lithium, sodium, potassium, and rubidium. 
     In certain embodiments, the solvent comprises methanol. In other embodiments, the solvent comprises water. In yet other embodiments, the reaction mixture is free of organic solvents. 
     In certain embodiments, the reaction mixture is kept at a temperature ranging from 0° C. to about 100° C. 
     In certain embodiments, the metal oxide comprises copper(II), magnesium(II), and aluminum (III). In yet other embodiments, the ratio of [copper(II)+magnesium(II)] to aluminum(III) is about 1.5:1 to about 6:1. In yet other embodiments, the ratio of [copper(II)+magnesium(II)] to aluminum(III) is about 3:1. In yet other embodiments, the ratio of copper(II) to magnesium (II) is about 1:9 to about 4:6. In yet other embodiments, the ratio of copper(II) to magnesium (II) is about 2:8. 
     In certain embodiments, the pressure of hydrogen gas used ranges from about 1 to 10 MPa. 
     In certain embodiments, the reaction is run for about 1 hour to about 24 hours. 
     In certain embodiments, the concentration of the α,β-unsaturated ketone in the reaction mixture is about 0.01-0.1 M. 
     In certain embodiments, the amount of the metal oxide used corresponds to about 1 to about 100 mol % in terms of the α,β-unsaturated ketone. 
     In certain embodiments, the reaction mixture is quenched by acidification. In other embodiments, the acidification comprises adding an acidic resin to the reaction mixture. In yet other embodiments, the resin comprises a weakly acidic or strongly acidic resin. In yet other embodiments, the quenched reaction mixture is purified by a separation method that separates solid material from the product-containing solution. In yet other embodiments, the separation method comprises decantation, filtration, and/or centrifugation. In yet other embodiments, the solid material is extracted at least once with an alcohol. In yet other embodiments, the alcohol comprises methanol or ethanol. In yet other embodiments, the at least one alcohol extract is combined with the product-containing solution. In yet other embodiments, the saturated ketone is isolated from the product-containing solution. In yet other embodiments, the isolation of the saturated ketone comprises extraction, evaporation, or concentration under vacuum. 
     In certain embodiments, the substitution at the 3-position of the ketone is optionally substituted aliphatic or optionally substituted aromatic. In certain embodiments, the substitution at the 1-position of the ketone is an optionally substituted (glycosyl)methyl group. 
     It is appreciated that where typical or preferred process conditions (i.e., reaction temperatures, times, mole ratios of reactants, solvents, pressures, and so forth) are given, other process conditions can also be used unless otherwise stated. Optimum reaction conditions can vary with the particular reactants or solvent used, but such conditions can be determined by one skilled in the art by routine optimization procedures. Those skilled in the art of organic synthesis will recognize that the nature and order of the synthetic steps presented can be varied for the purpose of optimizing the formation of the compounds described herein. 
     The processes described herein can be monitored according to any suitable method known in the art. For example, product formation can be monitored by spectroscopic means, such as nuclear magnetic resonance spectroscopy (e.g.,  1 H or  13 C), infrared spectroscopy, spectrophotometry (e.g., UV-visible), mass spectrometry, or by chromatography such as high pressure liquid chromatography (HPLC), gas chromatography (GC), gel-permeation chromatography (GPC), or thin layer chromatography (TLC). 
     The reactions or the processes described herein can be carried out in suitable solvents that can be readily selected by one skilled in the art of organic synthesis. Suitable solvents typically are substantially nonreactive with the reactants, intermediates, and/or products at the temperatures at which the reactions are carried out, i.e., temperatures that can range from the solvent&#39;s freezing temperature to the solvent&#39;s boiling temperature. A given reaction can be carried out in one solvent or a mixture of more than one solvent. Depending on the particular reaction step, suitable solvents for a particular reaction step can be selected. 
     Salts 
     The compounds described herein may form salts with acids or bases, and such salts are included in the present invention. The term “salts” embraces addition salts of free acids or bases that are useful within the methods of the invention. The term “pharmaceutically acceptable salt” refers to salts that possess toxicity profiles within a range that affords utility in pharmaceutical applications. In certain embodiments, the salts are pharmaceutically acceptable salts. 
     Suitable acid addition salts may be prepared from an inorganic acid or from an organic acid. Examples of inorganic acids include sulfate, hydrogen sulfate, hydrochloric, hydrobromic, hydriodic, nitric, carbonic, sulfuric, and phosphoric acids (including hydrogen phosphate and dihydrogen phosphate). Appropriate organic acids may be selected from aliphatic, cycloaliphatic, aromatic, araliphatic, heterocyclic, carboxylic and sulfonic classes of organic acids, examples of which include formic, acetic, propionic, succinic, glycolic, gluconic, lactic, malic, tartaric, citric, ascorbic, glucuronic, maleic, fumaric, pyruvic, aspartic, glutamic, benzoic, anthranilic, 4-hydroxybenzoic, phenylacetic, mandelic, embonic (or pamoic), methanesulfonic, ethanesulfonic, benzenesulfonic, pantothenic, sulfanilic, 2-hydroxyethanesulfonic, trifluoromethanesulfonic, p-toluenesulfonic, cyclohexylaminosulfonic, stearic, alginic, β-hydroxybutyric, salicylic, galactaric, galacturonic acid, glycerophosphonic acids and saccharin (e.g., saccharinate, saccharate). Salts may be comprised of a fraction of one, one or more than one molar equivalent of acid or base with respect to any compound of the invention. 
     Suitable base addition salts of compounds of the invention include, for example, ammonium salts and metallic salts including alkali metal, alkaline earth metal and transition metal salts such as, for example, calcium, magnesium, potassium, sodium and zinc salts. Pharmaceutically acceptable base addition salts also include organic salts made from basic amines such as, for example, N,N′-dibenzylethylene-diamine, chloroprocaine, choline, diethanolamine, ethylenediamine, meglumine (or N-methylglucamine) and procaine. All of these salts may be prepared from the corresponding compound by reacting, for example, the appropriate acid or base with the compound. 
     Definitions 
     As used herein, each of the following terms has the meaning associated with it in this section. 
     Unless defined otherwise, all technical and scientific terms used herein generally have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Generally, the nomenclature used herein and the laboratory procedures in animal pharmacology, pharmaceutical science, separation science and organic chemistry are those well-known and commonly employed in the art. It should be understood that the order of steps or order for performing certain actions is immaterial, so long as the present teachings remain operable. Moreover, two or more steps or actions can be conducted simultaneously or not. 
     As used herein, the articles “a” and “an” refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element. 
     As used herein, the term “alkoxy” employed alone or in combination with other terms means, unless otherwise stated, an alkyl group having the designated number of carbon atoms, as defined elsewhere herein, connected to the rest of the molecule via an oxygen atom, such as, for example, methoxy, ethoxy, 1-propoxy, 2-propoxy (or isopropoxy) and the higher homologs and isomers. A specific example is (C 1 -C 3 )alkoxy, such as, but not limited to, ethoxy and methoxy. 
     As used herein, the term “alkyl” by itself or as part of another substituent means, unless otherwise stated, a straight or branched chain hydrocarbon having the number of carbon atoms designated (i.e., C 1 -C 10  means one to ten carbon atoms) and includes straight, branched chain, or cyclic substituent groups. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tent-butyl, pentyl, neopentyl, hexyl, and cyclopropylmethyl. A specific embodiment is (C 1 -C 6 )alkyl, such as, but not limited to, ethyl, methyl, isopropyl, isobutyl, n-pentyl, n-hexyl and cyclopropylmethyl. 
     As used herein, the term “cycloalkyl” by itself or as part of another substituent refers to, unless otherwise stated, a cyclic chain hydrocarbon having the number of carbon atoms designated (i.e., C 3 -C 6  refers to a cyclic group comprising a ring group consisting of three to six carbon atoms) and includes straight, branched chain or cyclic substituent groups. Examples of (C 3 -C 6 )cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkyl rings can be optionally substituted. Non-limiting examples of cycloalkyl groups include: cyclopropyl, 2-methyl-cyclopropyl, cyclopropenyl, cyclobutyl, 2,3-dihydroxycyclobutyl, cyclobutenyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctanyl, decalinyl, 2,5-dimethylcyclopentyl, 3,5-dichlorocyclohexyl, 4-hydroxycyclohexyl, 3,3,5-trimethylcyclohex-1-yl, octahydropentalenyl, octahydro-1H-indenyl, 3a,4,5,6,7,7a-hexahydro-3H-inden-4-yl, decahydroazulenyl; bicyclo[6.2.0]decanyl, decahydronaphthalenyl, and dodecahydro-1H-fluorenyl. The term “cycloalkyl” also includes bicyclic hydrocarbon rings, non-limiting examples of which include, bicyclo-[2.1.1]hexanyl, bicyclo[2.2.1]heptanyl, bicyclo[3.1.1]heptanyl, 1,3-dimethyl[2.2.1]heptan-2-yl, bicyclo[2.2.2]octanyl, and bicyclo[3.3.3]undecanyl. 
     As used herein, the language “salt” refers to a salt of the administered compound prepared from acids and/or bases, including inorganic acids, inorganic bases, organic acids, inorganic bases, solvates (including hydrates) and clathrates thereof. 
     As used herein, the term “substituted” refers to that an atom or group of atoms has replaced hydrogen as the substituent attached to another group. 
     As used herein, the term “substituted alkyl” or “substituted cycloalkyl” refers to alkyl or cycloalkyl, as defined elsewhere herein, substituted by one, two or three substituents independently selected from the group consisting of halogen, —OH, alkoxy, tetrahydro-2-H-pyranyl, —NH 2 , —NH(C 1 -C 6  alkyl), —N(C 1 -C 6  alkyl) 2 , 1-methyl-imidazol-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, —C(═O)OH, —C(═O)O(C 1 -C 6 )alkyl, trifluoromethyl, —C(═O)NH 2 , —C(═O)NH(C 1 -C 6 )alkyl, —C(═O)N((C 1 -C 6 )alkyl) 2 , —SO 2 NH 2 , —SO 2 NH(C 1 -C 6  alkyl), —SO 2 N(C 1 -C 6  alkyl) 2 , —C(═NH)NH 2 , and —NO 2 , in certain embodiments containing one or two substituents independently selected from halogen, —OH, alkoxy, —NH 2 , trifluoromethyl, —N(CH 3 ) 2 , and —C(═O)OH, in certain embodiments independently selected from halogen, alkoxy and —OH. Examples of substituted alkyls include, but are not limited to, 2,2-difluoropropyl, 2-carboxycyclopentyl and 3-chloropropyl. 
     For aryl and heterocyclyl groups, the term “substituted” as applied to the rings of these groups refers to any level of substitution, namely mono-, di-, tri-, tetra-, or penta-substitution, where such substitution is permitted. The substituents are independently selected, and substitution may be at any chemically accessible position. In certain embodiments, the substituents vary in number between one and four. In other embodiments, the substituents vary in number between one and three. In yet another embodiments, the substituents vary in number between one and two. In yet other embodiments, the substituents are independently selected from the group consisting of C 1 -C 6  alkyl, —OH, C 1 -C 6  alkoxy, halo, amino, acetamido and nitro. As used herein, where a substituent is an alkyl or alkoxy group, the carbon chain may be branched, straight or cyclic. 
     Unless otherwise noted, when two substituents are taken together to form a ring having a specified number of ring atoms (e.g., R 2  and R 3  taken together with the nitrogen to which they are attached to form a ring having from 3 to 7 ring members), the ring can have carbon atoms and optionally one or more (e.g., 1 to 3) additional heteroatoms independently selected from nitrogen, oxygen, or sulfur. The ring can be saturated or partially saturated, and can be optionally substituted. 
     Whenever a term or either of their prefix roots appear in a name of a substituent the name is to be interpreted as including those limitations provided herein. For example, whenever the term “alkyl” or “aryl” or either of their prefix roots appear in a name of a substituent (e.g., arylalkyl, alkylamino) the name is to be interpreted as including those limitations given elsewhere herein for “alkyl” and “aryl” respectively. 
     In certain embodiments, substituents of compounds are disclosed in groups or in ranges. It is specifically intended that the description include each and every individual subcombination of the members of such groups and ranges. For example, the term “C 1-6  alkyl” is specifically intended to individually disclose C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 1 -C 6 , C 1 -C 5 , C 1 -C 4 , C 1 -C 3 , C 1 -C 2 , C 2 -C 6 , C 2 -C 5 , C 2 -C 4 , C 2 -C 3 , C 3 -C 6 , C 3 -C 5 , C 3 -C 4 , C 4 -C 6 , C 4 -C 5 , and C 5 -C 6  alkyl. 
     Ranges: throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual and partial numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range. 
     Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures, embodiments, claims, and examples described herein. Such equivalents were considered to be within the scope of this invention and covered by the claims appended hereto. For example, it should be understood, that modifications in reaction conditions, including but not limited to reaction times, reaction size/volume, and experimental reagents, such as solvents, catalysts, pressures, atmospheric conditions, e.g., nitrogen atmosphere, and reducing/oxidizing agents, with art-recognized alternatives and using no more than routine experimentation, are within the scope of the present application. 
     It is to be understood that, wherever values and ranges are provided herein, the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, all values and ranges encompassed by these values and ranges are meant to be encompassed within the scope of the present invention. Moreover, all values that fall within these ranges, as well as the upper or lower limits of a range of values, are also contemplated by the present application. The description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range and, when appropriate, partial integers of the numerical values within ranges. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range. 
     The following examples further illustrate aspects of the present invention. However, they are in no way a limitation of the teachings or disclosure of the present invention as set forth herein. 
     EXAMPLES 
     The invention is now described with reference to the following Examples. These 
     Examples are provided for the purpose of illustration only, and the invention is not limited to these Examples, but rather encompasses all variations that are evident as a result of the teachings provided herein. 
     It should be noted in certain protocols the term/unit “Vol” or “volume” or “volumes” is used to denote a relative amount of solvent volume to be used, and does not limit the scope of the invention in any manner. 
     General Experimental 
     Chemicals and solvents were purchased from Sigma-Aldrich, Alfa-Aesar, JT Baker or TCI and used as received. Compound 1a (Octulose) was obtained as a solution in H 2 O, and concentrated in vacuo before use. 
     All hydrogenation reactions under H 2  atmosphere were set-up in a 100 mL stainless-steel Parr reactor equipped with a mechanical stirrer. The reactions were pressurized under Hydrogen Atmosphere (Airgas, Ultra High Purity). The loaded reactor was placed on a bench-top Parr stand equipped with a Parr 4843 reactor controller. 
     Proton nuclear magnetic resonance (′H NMR) spectra were acquired using Agilent DD2 400 MHz, Agilent DD2 500 MHz, Agilent DD2 600 MHz or Varian Inova 500 MHz spectrometers. Chemical shifts (δ) are reported in parts per million (ppm) and are calibrated to the residual solvent peak. Coupling constants (J) are reported in Hz. Multiplicities are reported using the following abbreviations: s=singlet; d=doublet; t=triplet; m=multiplet (range of multiplet is given). Carbon nuclear magnetic resonance CC NMR) spectra were acquired using Agilent DD2 600 MHz or Agilent DD2 400 MHz spectrometer. Chemical shifts (δ) are reported in parts per million (ppm) and are calibrated to the residual solvent peak. 
     X-Ray Powder Diffraction (XRPD) measurements were performed on a Bruker D8-focus X-Ray diffractometer equipped with a Cu line-focus sealed tube, a divergent beam geometer and a NaI scintillation detector. Measurements were made with a 40 kV, 40 mA beam in the range 2θ from 3° to 80° locked couple scan type, a step size of 0.05° and a scan speed of 1 second/step. 
     Analytical thin layer chromatography was performed on pre-coated 250 μm layer thickness silica gel 60 F 254  Plates (EMD Chemicals Inc.). Visualization was performed by ultraviolet light and/or by staining with potassium permanganate or ceric ammonium molybdate (CAM) solutions. Purifications by column chromatography were performed using SilicaFlash F60 silica gel (40-63 μm, 230-400 mesh, Silicycle). 
     Elemental analyses were performed using inductively coupled plasma optical emission spectroscopy (ICP-OES) on a Perkin Elmer Optima 3000 equipped with a Scott nebulizer. The Sc standard was measured at 361.384 nm, Cu at 324.754 nm, Mg at 279.079 nm and Al at 308.215 nm. Samples were prepared for ICP-OES by dissolving a known solid amount in 2 mL of 6 M nitric acid and diluting to 50 mL with DI H 2 O. 
     Elemental components were quantified by comparison with purchased calibration standards. High resolution mass spectra (HRMS) were recorded using an Agilent 6550A QTOF by electrospray ionization time of flight experiments. 
     Example 1 
     A. Synthesis of the Cu-PMO Catalyst 
     A solution of Al(NO 3 ) 3 .9H 2 O (18.8 g, 0.05 mol, 1 equiv.), Mg(NO 3 ) 2 .6H 2 O (30.76 g, 0.12 mol, 2.4 equiv.) and Cu(NO 3 ) 2 .2.5H 2 O (7.0 g, 0.03 mol, 0.6 equiv.) in 300 mL distilled (DI) water was added dropwise over four hours to a stirring solution of Na 2 CO 3 .H 2 O (6.2 g, 0.05 mol, 1 equiv.) in 375 mL distilled water. The pH was kept constant at pH ˜10 by adding aliquots of 1 M NaOH aqueous solution. Upon completion of the addition, the mixture was allowed to stir vigorously at room temperature for three days. The blue precipitate was collected by vacuum filtration and washed with 1.5 L distilled water. The filter cake was then suspended in a solution of Na 2 CO 3  solution (62 g, 0.5 mol, 10 equiv.) in DI H 2 O (250 mL, 2M) and allowed to stir at room temperature overnight. Upon completion, the precipitate was collected by vacuum filtration and washed with DI H 2 O (2.5 L). The filter was left to dry overnight in a 105° C. oven to obtain copper-doped hydrotalcite. The solid was ground by mortar and pestle and subjected to calcination at 460° C. in air for 24 h to obtain Cu-PMO (9.21 g) as a green powder. The Cu-PMO was analyzed by XRPD ( FIG. 5 ), showing the expected loss of hydrotalcite features. Elemental analysis of Cu-PMO was performed by ICP-OES (Table 2) and confirms incorporation of the metals in the expected ratio. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Metal Ion Composition of Cu-PMO determined by ICP-OES 
               
            
           
           
               
               
               
               
            
               
                   
                 Cu 
                 Mg 
                 Al 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Concentration (mg/L) 
                 26.09 
                 39.37 
                 19.36 
               
               
                   
                 Mass in solution (mg) 
                 1.305 
                 1.969 
                 0.968 
               
               
                   
                 Amount in solution (mmol) 
                 0.0205 
                 0.0806 
                 0.0359 
               
               
                   
                 Normalized Ratio of Metals 
                 0.57 
                 2.25 
                 1.00 
               
               
                   
                   
               
            
           
         
       
     
     B. Synthesis of the Hydrotalcite (HTC) Catalyst 
     A solution of Al(NO 3 ) 3 .9H 2 O (18.8 g, 0.05 mol, 1 equiv.) and Mg(NO 3 ) 2 .6H 2 O (38.46 g, 0.15 mol, 3 equiv.) in 300 mL distilled (DI) water was added dropwise over four hours to a stirring solution of Na 2 CO 3 .H 2 O (6.2 g, 0.05 mol, 1 equiv.) in 375 mL distilled water. The pH was kept constant at pH ˜10 by adding aliquots of 1 M NaOH aqueous solution. Upon completion of the addition, the mixture is allowed to stir vigorously at 40° C. for three days. The white precipitate is collected by vacuum filtration and washed with 1.5 L distilled water. The filter cake is then suspended in a solution of Na 2 CO 3  solution (62 g, 0.5 mol, 10 equiv.) in DI H 2 O (250 mL, 2M) and allowed to stir at 40° C. overnight. Upon completion, the precipitate is collected by vacuum filtration and washed with DI H 2 O (2.5 L). The filter is left to dry overnight in a 105° C. oven to obtain hydrotalcite (HTC). The HTC was analyzed by XRPD ( FIG. 6 ) and is identical to literature reports (Villadsen, et al., 2017, ChemBioChem 18:574-612). 
     C. Synthesis of Lubineau&#39;s Ketone 1b 
     
       
         
         
             
             
         
       
     
     Synthesis of Nonulose 1b was performed according to a modified procedure by Cavezza et al. (Lalitha, et al., 2015, Carbohydr. Res. 402:158-171). D-(+)-Glucose (10 g, 55.51 mmol, 1 equiv.) and 2,4-pentanedione (6.8 mL, 6.65 g, 66.53 mmol, 1.2 equiv.) were added to a 100 mL round bottom flask equipped with a Teflon coated stir bar. MeOH (20.7 mL) was added by syringe. A solution of NaOH (3.33 g, 83.25 mmol, 15 equiv.) in MeOH (22 mL) and H 2 O (10 mL) was prepared. After full dissolution of NaOH, the solution was added to the round bottom flask by pouring. The mixture was allowed to stir at room temperature for two days. Upon completion, the flask was placed in an ice bath and the basic mixture was quenched by dropwise addition of concentrated HCl (6.8 mL). The resulting crude mixture was evaporated in vacuo to obtain the crude product. Column chromatography (silica gel, EtOAc:MeOH:H 2 O, 30:8:2) furnished pure product 1b as a brown oil in 82% yield (11.284 g, 45.46 mmol). 
     R f =0.14 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 3.77 (dd, J=12.0, 2.1 Hz, 1H), 3.61 (ddd, J=20.2, 10.6, 5.7 Hz, 2H), 3.37-3.17 (m, 3H), 3.05 (t, J=9.1 Hz, 1H), 2.86 (dd, J=16.0, 3.0 Hz, 1H), 2.57 (dd, J=16.0, 9.1 Hz, 1H), 2.18 (s, 3H).  13 C NMR (101 MHz, CD 3 OD) δ 208.83, 80.24, 78.19, 75.84, 73.69, 70.30, 61.38, 45.76, 29.19. Analytical data is identical to that reported in Gonzalez, et al., 1986, Carbohydr. Res. 158:53-66. 
     D. General Procedure a for Synthesis of C-Glycosidic Substrates 2a-g 
     
       
         
         
             
             
         
       
     
     The procedure developed by de Winter et al. was replicated with alterations to afford targeted substrates (Auge &amp; Lubin-Germain, 2014, Carbohydr. Chem. 40:11-30). The hygroscopicity of the starting material varied the true amount weighed out. Hence, an internal standard (biphenyl) was utilized to quantify amount of starting material added by  1 H NMR, which is used to correct product yields. It follows that this variation in starting material content affects the relative amounts of reagents and reactants. C-glycoside ketone 1a-b (1 equiv.) was added to a round bottom flask equipped with a Teflon coated stir bar. MeOH (0.45 M) and biphenyl (0.05 equivalents, internal standard) were added by syringe and the mixture was stirred until complete dissolution of the starting material. An aliquot was removed and analyzed by  1 H NMR to determine the amount of C-glycoside 1a-b added. L-Proline (1 equiv.), benzylic aldehyde (1.1 equiv.) and MgO (10 wt % of C-glycoside) were added to the stirring mixture. The reaction was allowed to proceed at 50° C. with stirring until completion as observed by TLC analysis. The mixture was filtered over filter paper, then mixed with silica gel and concentrated in vacuo. Crude product was purified over a short-path silica plug, after dry loading, by first flushing the internal standard (biphenyl) and excess aldehyde with a small amount of ethyl acetate, then collecting product with acetone as liquid phase. 
     E. General Procedure B for Synthesis of C-Glycosidic Substrates 2i-j 
     
       
         
         
             
             
         
       
     
     The procedure developed by Foley et al. was replicated with minor alterations to afford aliphatic C-glycosidic enones (Rodrigues, et al., 2000, Chem. Commun. 0:2049-2050). C-glycoside ketone 1a (1 equiv.) and biphenyl (0.05 equiv., internal standard) were added to a round bottom flask equipped with a Teflon coated stir bar. DMF (2.4 M) was added by syringe and the mixture was stirred until complete dissolution of the starting material. An aliquot was removed for  1 H NMR analysis of starting material amount. Then, hexanes (2 M), pyrrolidine (1 equiv.) and aliphatic aldehyde (1 equiv.) were added to the stirring mixture. The reaction was allowed to proceed at room temperature with stirring until completion as observed by TLC analysis. The mixture was treated with Amberlite IR-120 H+ resin, filtered, and concentrated in vacuo. Crude product was purified by column chromatography (silica gel, 450:50 DCM:MeOH). 
     F. Optimized General Procedure C for Full Catalytic Hydrogenation of C-Glycosidic Enones 2a-j 
     
       
         
         
             
             
         
       
     
     C-glycosidic enone 2a-j (0.5 mmol, 1 equiv.) was added to a 25 mL round-bottom flask equipped with a Teflon coated stir bar. H 2 O (10 mL, 0.05 M) was added by syringe. Cu-PMO (see below section 1i. for amounts) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) were added to the mixture in single portions. The mixture was allowed to stir at reflux (100° C.) for 5 hours. Upon completion, the mixture was cooled and treated with Amberlite IR-120 H+ resin. The heterogeneous mixture was filtered over cellulose filter paper and the retentate was washed with methanol (˜20 mL). The combined organic fractions were concentrated in vacuo. CHCl 3  (0.04 mL, 59.69 mg, 0.5 mmol, 1 equiv., internal standard) were added to the residue, and the mixture was completely dissolved in deuterated methanol for  1 H and  11 B NMR analysis. If boron salts were present, the mixture was re-dissolved in methanol and evaporated in vacuo, and the process was repeated until the absence of boron salts was confirmed by NMR. Once the NMR yield was obtained and the absence of boron salts was confirmed by NMR, the mixture was evaporated in vacuo and placed under high vacuum before weighing (if complete conversion to desired product). When desired, produced diastereomers were separated by column chromatography (silica gel, 450:50 DCM:MeOH). 
     G. Procedures and Amounts for Enone Full Reduction (c.f. Table 1) 
     Optimization of the reduction of enone under H 2  pressure was performed according to the following representative procedure D: C-Glycosidic enone 2a (1 equiv.) was added to a 100 mL stainless-steel Parr reactor. NaBH 4 , and Cu-PMO catalyst were added to the Parr reactor (see Table 3 for amounts). Solvent was added to the reactor by syringe. The reactor was closed once all reaction components were added and subsequently pressurized under H 2  pressure. The reactor was placed on a stand and connected to a temperature controller. Heating was turned on at time t=0. The reaction was allowed to stir for the targeted amount of time (see Table 3). Upon completion, the reactor was cooled to room temperature under a stream of water. Once cool, the reactor was depressurized and opened in a fumehood. Flammable gas is then released. The mixture was treated with Amberlite IR-120H+ resin and filtered over cellulose paper before concentrating in vacuo. DMF or CHCl 3  (1 equiv., internal standard) was added to the residue, and the mixture was completely dissolved in deuterated methanol for  1 H NMR analysis. 
     Optimization of the reduction of enone without H 2  pressure was performed according to the following representative procedure E: C-glycosidic enone 2a (1 equiv.) was added to a 25 mL round-bottom flask equipped with a Teflon coated stir bar. Solvent was added by syringe. NaBH 4  and Cu-PMO catalyst were added to the mixture in single portions. The mixture was allowed to stir at the chosen temperature for a set amount of time (Table 3). Upon completion, the mixture was brought to room temperature and treated with Amberlite IR-120 H+ resin. The heterogeneous mixture was filtered over cellulose filter paper and the retentate was washed with methanol. The combined organic fractions were concentrated in vacuo. DMF or CHCl 3  (1 equiv., internal standard) was added to the residue, and the mixture was completely dissolved in deuterated methanol for  1 H NMR analysis. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Amounts in each reaction towards the Cu-catalyzed full reduction of enones (c.f. Table 1) 
               
            
           
           
               
               
               
               
               
               
            
               
                 Entry from 
                   
                   
                   
                   
                 Internal 
               
               
                 Table 1 
                 Compound 2a 
                 Catalyst 
                 Additive 
                 Solvent 
                 Standard 
               
               
                   
               
               
                 1 
                 0.3 mmol, 
                 Cu-PMO 10 
                 NaBH 4  (0.6 mmol, 
                 MeOH (30 mL, 
                 DMF (23 μL, 
               
               
                   
                 83.5 mg 
                 mg 
                 22.7 mg) 
                 0.01M) 
                 1 eq.) 
               
               
                 2 
                 1.5 mmol, 
                 Cu-PMO 55 
                 NaBH 4  (3.0 mmol, 
                 MeOH (30 mL, 
                 DMF (110 μL, 
               
               
                   
                 417.5 mg 
                 mg 
                 113.5 mg) 
                 0.05M) 
                 1 eq.) 
               
               
                 3 
                 1.5 mmol, 
                 Cu-PMO 55 
                 NaBH 4  (3.0 mmol, 
                 MeOH (30 mL, 
                 DMF (110 μL, 
               
               
                   
                 417.5 mg 
                 mg 
                 113.5 mg) 
                 0.05M) 
                 1 eq.) 
               
               
                 4 
                 1.5 mmol, 
                 Cu-PMO 55 
                 NaBH 4  (3.0 mmol, 
                 MeOH (30 mL, 
                 DMF (110 μL, 
               
               
                   
                 417.5 mg 
                 mg 
                 113.5 mg) 
                 0.05M) 
                 1 eq.) 
               
               
                 5 
                 1.5 mmol, 
                 Cu-PMO 55 
                 NaBH 4  (3.0 mmol, 
                 MeOH (30 mL, 
                 DMF (110 μL, 
               
               
                   
                 417.5 mg 
                 mg 
                 113.5 mg) 
                 0.05M) 
                 1 eq.) 
               
               
                 6 
                 0.725 mmol, 
                 Cu-PMO 26.5 
                 NaBH 4  (1.45 mmol, 
                 H 2 O (14.5 mL, 
                 DMF (56 μL, 
               
               
                   
                 201.8 mg 
                 mg 
                 55 mg) 
                 0.05M) 
                 1 eq.) 
               
               
                 7 
                 1.5 mmol, 
                 Cu-PMO 55 
                 NaBH 4  (3.0 mmol, 
                 H 2 O (30 mL, 
                 DMF (110 μL, 
               
               
                   
                 417.5 mg 
                 mg 
                 113.5 mg) 
                 0.05M) 
                 1 eq.) 
               
               
                   
               
            
           
         
       
     
     H. Procedure for Large-Scale Reduction of Aromatic Enone 2e 
     C-glycosidic enone 2e (8.12 g, 25 mmol, 1 equiv.) and water (500 ml, 0.05 M) were charged to a 1 L double-jacketed reactor equipped with a mechanical stirrer. To this suspension were added Cu-PMO (892 mg, 11 mol %) and NaBH 4  (1.89 g, 50 mmol, 2 equiv.) in single portions. The reaction mixture was allowed to stir at reflux (100° C.) for 5 hours. Upon completion, the dark brown homogeneous solution was cooled and treated with Amberlite IR-120 H+ resin (˜180 g). The suspension was filtered over cellulose filter paper and the retentate was washed with methanol (˜1 L). The combined organic and aqueous fractions were evaporated to dryness under vacuum. The crude residue was purified by filtration over silica (eluting with EtOAc:MeOH 80:20), followed by a carbon black treatment at reflux in ethanol for one hour. After concentration in vacuo, the solid was diluted with water, filtered, and lyophilized, furnishing pure product 3e (mixture of diastereomers) as a beige powder in 72.9% isolated yield (6 g, 18.27 mmol).  1 H and  13 C NMR data are consistent with those from the smaller scale results reported in Section I. 
     I. Catalyst Recycling Studies 
     C-glycosidic enone 2e (162.2 mg, 0.5 mmol, 1 equiv.) was added to a 25 mL round-bottom flask equipped with a Teflon coated stir bar. H 2 O (10 mL, 0.05 M) was added by syringe. Cu-PMO (Trial 1: 16.5 mg, 10 wt % and afterwards as recovered from previous run) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) were added to the mixture in single portions. The mixture was allowed to stir at reflux (100° C.) for 5 hours. Upon completion, the mixture was cooled and treated with Amberlite IR-120 H+ resin. The heterogeneous mixture was filtered over cellulose filter paper and the retentate was washed with methanol (˜20 mL). The combined organic fractions were concentrated in vacuo. CHCl 3  (0.04 mL, 59.69 mg, 0.5 mmol, 1 equiv., internal standard) were added to the residue, and the mixture was completely dissolved in deuterated methanol for  1 H and  11 B NMR analysis. Once the NMR yield was obtained and the absence of boron salts was confirmed by NMR, the mixture was evaporated in vacuo and placed under high vacuum before weighing to obtain the isolated yield. The recovered catalyst was placed in a dessicator until further use. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Product yields after catalyst recycling 
               
            
           
           
               
               
               
               
            
               
                   
                 2e Conversion a   
                 NMR Yield 3e/3e′ a   
                 Isolated Yield 3e/3e′ 
               
               
                   
                 (%) 
                 (%) 
                 (%) 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                 Cycle 1 
                 100 
                 &gt;95 
                 93 
               
               
                 Cycle 2 
                 100 
                 94 
                 97 
               
               
                 Cycle 3 
                 100 
                 &gt;95 
                 85 
               
               
                 Cycle 4 
                 100 
                 &gt;95 
                 92 
               
               
                 Cycle 5 
                 100 
                 &gt;95 
                 93 
               
               
                   
               
               
                   a Conversion and NMR yields determined by  1 H NMR using CHCl 3  as internal standards. 
               
            
           
         
       
     
     J. Amberlite IR-120H +  Regeneration and Reuse 
     Amberlite IR-120 H+ can be recuperated after reaction through a simple vacuum filtration. After recuperation, Amberlite IR-120 H +  can be reused after treatment to regenerate its acidity. To do so, spent Amberlite IR-120 H+ is placed in an Erlenmeyer containing a Teflon coated stir bar. The solid was covered with concentrated sulfuric acid and allowed to stir at room temperature for 30 minutes. After completion, the resin was filtered out of the solution and washed with DI water. The resin was placed in a dessicator for further drying until use. 
     Use of recycled resin did not alter reduction results. 2a (0.5 mmol) was reduced using our optimized conditions with Cu-PMO (11 wt %) and NaBH 4  (2 equiv.) in MeOH (0.05 M) at 100° C. for 5 hours. After completion, recycled Amberlite IR-120 H +  resin was added to the mixture to acidify until pH=5. The mixture was filtered, washed with MeOH, and evaporated in vacuo to generate product 3a, as a diastereomeric mixture, in &gt;95% NMR yield. 
     K. Substrates Syntheses, Isolations and Characterizations 
     1. C-Glycosidic Aromatic Enones 2a-h 
     
       
         
         
             
             
         
       
     
     2a was synthesized following general procedure A with Octulose 1a (1125 mg, 5.918 mmol), benzaldehyde (0.85 mL, 921.1 mg, 8.68 mmol), L-Proline (908.5 mg, 7.891 mmol), biphenyl (61.4 mg, internal standard), and MgO (150 mg) in methanol (17.5 mL). Crude product was isolated from internal standard, L-proline and excess aldehyde by short path silica plug (EtOAc, then acetone) to obtain 2a as an off-white solid in 85% isolated yield. 
     R f =0.32 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.65-7.56 (m, 3H), 7.42-7.33 (m, 3H), 6.84 (d, J=16.3 Hz, 1H), 3.77 (dd, J=11.1, 5.4 Hz, 1H), 3.64 (t, J=9.4, 1H), 3.42 (dd, J=10.5, 8.9, 1H), 3.27 (t, J=3.2, 1H), 3.17-3.02 (m, 3H), 2.84 (dd, J=15.8, 9.2 Hz, 1H);  13 C NMR (151 MHz, CD 3 OD) δ 199.98, 143.97, 135.11, 130.85, 129.19, 128.67, 126.66, 78.95, 77.65, 74.31, 70.67, 70.18, 43.36. HR-MS (ESI + , m/z): Calcd for C 14 H 9 O 5  [M+H] +  279.12325 Found 279.12345. Analytical data is identical to that reported in Anastas &amp; Warner,  Green Chemistry: Theory and Practice , Oxford University Press, Oxford, 1998. 
     
       
         
         
             
             
         
       
     
     2b was synthesized following general procedure A with Octulose 1a (324.9 mg, 1.710 mmol), 2-methylbenzaldehyde (0.34 mL, 347.23 mg, 2.89 mmol), L-Proline (302.8 mg, 2.63 mmol), biphenyl (23.6 mg, 0.123 mmol) and MgO (50 mg) in methanol (5.8 mL). Crude product was isolated from internal standard, L-proline and excess aldehyde by short path silica plug (Ethyl acetate, then acetone) to obtain 2b as a yellow oil in 86% isolated yield. 
     R f =0.36 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.93 (d, J=16.0 Hz, 1H), 7.63 (d, J=7.6 Hz, 1H), 7.34-7.24 (m, 1H), 7.24-7.11 (m, 2H), 6.77 (d, J=16.0 Hz, 1H), 3.80 (dd, J=11.1, 5.4 Hz, 1H), 3.66 (td, J=9.4, 2.5 Hz, 1H), 3.49-3.40 (m, 1H), 3.33-3.24 (m, 1H), 3.19-3.05 (m, 3H), 2.84 (dd, J=15.8, 9.2 Hz, 1H), 2.42 (s, 3H).  13 C NMR (101 MHz, CD 3 OD) δ 199.43, 140.75, 137.97, 133.17, 130.43, 130.06, 126.92, 126.09, 126.01, 78.34, 77.13, 73.69, 70.07, 69.61, 43.09, 18.29. HR-MS (ESI + , m/z): Calcd for C 16 H 21 O 5  [M+H] +  293.13890 Found 293.13829. 
     
       
         
         
             
             
         
       
     
     2c was synthesized following general procedure A with Octulose 1a (349.9 mg, 1.841 mmol), 2-methoxybenzaldehyde (0.35 mL, 394 mg, 2.89 mmol), L-Proline (302.8 mg, 2.63 mmol), biphenyl (21.0 mg, 0.136 mmol, internal standard) and MgO (50 mg) in methanol (5.8 mL). Crude product was isolated from internal standard, L-proline and excess aldehyde by short path silica plug (Ethyl acetate, then acetone) to obtain 2c as a brown solid in 77% isolated yield. 
     R f =0.60 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.94 (d, J=16.4 Hz, 1H), 7.61 (dd, J=7.7, 1.7 Hz, 1H), 7.38 (ddd, J=8.8, 7.4, 1.7 Hz, 1H), 7.03 (dd, J=8.5, 1.0 Hz, 1H), 6.96 (td, J=7.5, 1.0 Hz, 1H), 6.89 (d, J=16.3 Hz, 1H), 3.89 (s, 3H), 3.83-3.75 (m, 2H), 3.66 (td, J=9.4, 2.5 Hz, 1H), 3.44 (ddd, J=10.6, 9.0, 5.4 Hz, 1H), 3.20-3.02 (m, 3H), 2.82 (dd, J=15.9, 9.3 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 199.78, 158.65, 138.52, 131.86, 128.16, 126.18, 122.92, 120.43, 111.02, 78.34, 77.05, 73.70, 70.08, 69.59, 54.68, 42.76. HR-MS (ESI + , m/z): Calcd for C 16 H 21 O 6  [M+H] +  309.13381 Found 309.13310. 
     
       
         
         
             
             
         
       
     
     2d was synthesized following general procedure A with Octulose 1a (349.9 mg, 1.841 mmol), 4-methoxybenzaldehyde (0.35 mL, 394 mg, 2.89 mmol), L-Proline (302.8 mg, 2.63 mmol), biphenyl (20.3 mg, 0.132 mmol, internal standard) and MgO (50 mg) in methanol (5.8 mL). Crude product was isolated from internal standard, L-proline and excess aldehyde by short path silica plug (Ethyl acetate, then acetone) to obtain 2d as an off-white solid in 79% isolated yield. 
     R f =0.34 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.64-7.52 (m, 3H), 6.94 (dd, J=9.1, 2.5 Hz, 2H), 6.72 (d, J=16.1, 1H), 3.83-3.71 (m, 4H), 3.64 (td, J=9.4, 2.5 Hz, 1H), 3.53-3.40 (m, 1H), 3.30-3.21 (m, 1H), 3.19-2.98 (m, 3H), 2.87-2.73 (m, 1H);  13 C NMR (151 MHz, CD 3 OD) δ 199.75, 162.17, 143.79, 130.21, 127.19, 123.98, 114.31, 78.61, 77.37, 73.97, 70.32, 69.80, 54.74, 42.89. HR-MS (ESI + , m/z): Calcd for C 16 H 21 O 6  [M+H] +  309.13381 Found 309.13324. Analytical data is identical to that reported in Cipolla, et al., 2002, Biorg. Med. Chem. 10:1639-1646. 
     
       
         
         
             
             
         
       
     
     2e was synthesized following general procedure A with Octulose 1a (1500 mg, 7.891 mmol, 1 equiv.), vanillin (1320.2 mg, 8.68 mmol, 1.1 equiv.), L-Proline (908.5 mg, 7.891 mmol, 1 equiv.) and HTC (150 mg, 10 wt %) in methanol (17.5 mL). Pure product precipitated out of the reaction mixture and was filtered to obtain 2e as an off-white solid in 63% isolated yield. 
     R f =0.24 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.57 (d, J=16.1 Hz, 1H), 7.21 (d, J=1.9 Hz, 1H), 7.11 (dd, J=8.2, 2.0 Hz, 1H), 6.80 (d, J=8.2 Hz, 1H), 6.71 (d, J=16.1 Hz, 1H), 3.88 (s, 3H), 3.79 (dd, J=11.1, 5.4 Hz, 1H), 3.65 (td, J=9.4, 2.6 Hz, 1H), 3.44 (ddd, J=10.5, 8.9, 5.3 Hz, 1H), 3.29 (p, J=1.6 Hz, 1H), 3.17-3.00 (m, 3H), 2.82 (dd, J=15.7, 9.3 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 199.58, 147.98, 144.38, 126.30, 123.26, 123.13, 115.11, 110.42, 78.36, 77.20, 73.76, 70.08, 69.58, 54.97, 42.58. HR-MS (ESI + , m/z): Calcd for C 16 H 21 O 7  [M+H] +  325.12873 Found 325.12751. Analytical data is identical to that reported in Cipolla, et al., 2002, Biorg. Med. Chem. 10:1639-1646. 
     
       
         
         
             
             
         
       
     
     2f was synthesized following general procedure A with Octulose 1a (624.9 mg, 3.285 mmol), 4-trifluoromethylbenzaldehyde (0.67 mL, 854.3 mg, 4.906 mmol), L-Proline (506.6 mg, 4.400 mmol), biphenyl (19.8 mg, 0.128 mmol, internal standard) and MgO (50 mg) in methanol (9.8 mL). Crude product was isolated from internal standard, L-proline and excess aldehyde by short path silica plug (Ethyl acetate, then acetone) to obtain 2f as a brown solid in 71% isolated yield. 
     R f =0.37 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.81 (d, J=8.1 Hz, 2H), 7.72-7.61 (m, 3H), 6.97 (d, J=16.3 Hz, 1H), 3.79 (dd, J=11.1, 5.4 Hz, 1H), 3.67 (td, J=9.4, 2.7 Hz, 1H), 3.44 (ddd, J=10.5, 8.9, 5.4 Hz, 1H), 3.20-3.05 (m, 4H), 2.87 (dd, J=15.9, 9.2 Hz, 1H).  13 C NMR (151 MHz, CD 3 OD) δ 199.01, 141.04, 138.41, 138.40, 128.51, 131.61, 131.39, 131.18, 130.96, 128.48, 125.48, 125.44, 125.41, 125.39, 78.35, 76.98, 73.70, 70.07, 69.60, 43.01. HR-MS (ESI + , m/z): Calcd for C 16 H 18 F 3 O 5  [M+H] +  347.11063 Found 347.10976. 
     
       
         
         
             
             
         
       
     
     2g was synthesized following general procedure A with Octulose 1a (500 mg, 2.63 mmol), 2-fluorobenzaldehyde (0.45 mL, 530.1 mg, 4.271 mmol), L-Proline (455 mg, 3.952 mmol), biphenyl (19.9 mg, 0.128 mmol, internal standard) and MgO (75 mg) in methanol (8.8 mL). Crude product was isolated from internal standard, L-proline and excess aldehyde by short path silica plug (Ethyl acetate, then acetone) to obtain 2g as a yellow solid in 93% isolated yield. 
     R f =0.37 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.76-7.68 (m, 2H), 7.43 (dddd, J=8.5, 7.2, 5.3, 1.7 Hz, 1H), 7.25-7.11 (m, 2H), 6.94 (d, J=16.3 Hz, 1H), 3.79 (dd, J=11.1, 5.4 Hz, 1H), 3.66 (td, J=9.4, 2.6 Hz, 1H), 3.44 (ddd, J=10.5, 8.9, 5.4 Hz, 1H), 3.29 (dt, J=3.1, 1.5 Hz, 1H), 3.17-3.04 (m, 3H), 2.83 (dd, J=15.9, 9.2 Hz, 1H).  13 C NMR (151 MHz, CD 3 OD) δ 199.14, 162.30, 160.63, 135.03, 135.01, 132.07, 132.01, 128.76, 128.74, 128.21, 128.17, 124.49, 124.47, 122.31, 122.24, 115.72, 115.58, 78.33, 76.99, 73.67, 70.06, 69.59, 43.09. HR-MS (ESI + , m/z): Calcd for C 15 H 18 FO 5  [M+H] +  297.11383 Found 297.11360. 
     
       
         
         
             
             
         
       
     
     2h was synthesized following general procedure A with Nonulose 1b (106.3 mg, 0.483 mmol), benzaldehyde (0.23 mL, 235 mg, 2.21 mmol), L-Proline (232 mg, 2.01 mmol), biphenyl (16.4 mg, 0.106 mmol, internal standard) and MgO (50 mg) in methanol (4.5 mL). Crude product was isolated from internal standard, L-proline and excess aldehyde by short path silica plug (Ethyl acetate, then acetone) to obtain 2h as a beige powder in 66% isolated yield. 
     R f =0.18 (silica gel, 9:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.67-7.61 (m, 3H), 7.42-7.37 (m, 3H), 6.90 (d, J=16.2 Hz, 1H), 3.80-3.71 (m, 2H), 3.64-3.58 (m, 1H), 3.38-3.31 (m, 2H), 3.21 (ddd, J=9.3, 5.1, 2.3 Hz, 1H), 3.18-3.06 (m, 2H), 2.89 (dd, J=15.9, 8.9 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 199.56, 143.40, 134.56, 130.24, 128.59, 128.10, 126.03, 80.19, 78.29, 76.03, 73.70, 70.24, 61.3, 42.92. Analytical data is identical to that reported in Auge &amp; Lubin-Germain, 2014, Carbohydr. Chem. 40:11-30. 
     2. Aliphatic C-glycosidic Enones 21-j 
     
       
         
         
             
             
         
       
     
     2i was synthesized following general procedure B with Octulose 1a (1000 mg, 5.26 mmol, 1 equiv.), pyrrolidine (0.44 mL, 374.1 mg, 5.26 mmol, 1 equiv.) and hexanal (0.64 mL, 526.8 mg, 5.26 mmol, 1 equiv.) in hexanes (2.68 mL) and DMF (2.2 mL) at room temperature overnight. The crude mixture was purified by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 2i as an orange oil in 36% yield. 
     R f =0.43 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 6.91 (dt, J=15.8, 7.0 Hz, 1H), 6.13 (dt, J=15.9, 1.5 Hz, 1H), 3.76 (dd, J=11.1, 5.4 Hz, 1H), 3.58 (td, J=9.4, 2.5 Hz, 1H), 3.42 (ddd, J=10.6, 8.9, 5.4 Hz, 1H), 3.31-3.21 (m, 1H), 3.14-3.02 (m, 2H), 2.99-2.89 (m, 1H), 2.71 (dd, J=15.9, 9.3 Hz, 1H), 2.28-2.19 (m, 2H), 1.54-1.43 (m, 2H), 1.42-1.23 (m, 4H), 0.97-0.85 (m, 3H).  13 C NMR (101 MHz, CD 3 OD) δ 201.24, 150.63, 131.87, 79.99, 78.59, 75.30, 71.71, 71.21, 43.61, 33.74, 32.74, 29.12, 23.71, 14.54. HR-MS (ESI + , m/z): Calcd for C 14 H 25 O 5  [M+H] +  273.17020 Found 273.16922. 
     
       
         
         
             
             
         
       
     
     2j was synthesized following general procedure B with Octulose 1a (250 mg, 1.315 mmol, 1 equiv.), pyrrolidine (0.11 mL, 93.5 mg, 1.315 mmol, 1 equiv.) and isobutyraldehyde (0.12 mL, 94.8 mg, 1.315 mmol, 1 equiv.) in heptane (0.66 mL) and DMF (0.55 mL) at room temperature overnight. The crude mixture was purified by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 2j (mixture of trans isomer 2j and deconjugated isomer 2j′) as an orange oil in 70% yield. HR-MS (ESI + , m/z): Calcd for C 12 H 21 O 5  [M+H] +  245.13890 Found 245.13824. 
     2j: R f =0.5 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 6.87 (dd, J=16.0, 6.8 Hz, 1H), 6.09 (dd, J=16.0, 1.4 Hz, 1H), 3.77 (dt, J=11.1, 5.5 Hz, 1H), 3.57 (dtd, J=14.5, 9.4, 2.7 Hz, 1H), 3.41 (dddd, J=10.7, 8.9, 5.4, 1.9 Hz, 1H), 3.24 (dt, J=8.9, 4.5 Hz, 1H), 3.08 (m, 2H), 2.94 (dd, J=16.0, 2.5 Hz, 1H), 2.72 (dd, J=16.0, 9.3 Hz, 1H), 2.59-2.42 (m, 1H), 1.07 (d, J=6.8 Hz, 6H).  13 C NMR (101 MHz, CD 3 OD) δ 201.26, 156.10, 128.85, 79.77, 78.29, 75.07, 71.48, 70.99, 43.49, 32.44, 21.62. 
     2j′: R f =0.5 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 5.26 (dddd, J=8.6, 7.2, 2.9, 1.5 Hz, 1H), 3.77 (dt, J=11.1, 5.5 Hz, 1H), 3.57 (dtd, J=14.5, 9.4, 2.7 Hz, 1H), 3.41 (dddd, J=10.7, 8.9, 5.4, 1.9 Hz, 1H), 3.17 (d, J=7.3 Hz, 2H), 3.08 (m, 2H) 2.83 (dd, J=15.9, 2.9 Hz, 1H), 2.59-2.42 (m, 1H), 1.67 (dd, J=46.4, 1.4 Hz, 6H).  13 C NMR (101 MHz, CD 3 OD) δ 210.04, 136.69, 117.02, 79.71, 78.18, 75.05, 71.46, 70.97, 45.83, 44.04, 25.83, 18.08. 
     3. C-Glycosidic Alcohols 3a-j and 3a′-j′ 
     
       
         
         
             
             
         
       
     
     3a and 3a′ were synthesized following general procedure C with 2a (139.2 mg, 0.5 mmol, 1 equiv.), Cu-PMO (16.5 mg, 11 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL) at reflux for 5 hours. The mixture containing only 3a and 3a′ was fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show 89% isolated yield. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3a and 3a′ as clear oils in 10% yield for each. 
     Mixture HR-MS (ESI + , m/z): Calcd for C 15 H 23 O 5  [M+H] +  283.15455 Found 283.15364. 3a R f =0.6 (silica gel, 8:1 DCM:MeOH, developed with CAM);  1 H NMR (400 MHz, CD 3 OD) δ 7.26-7.15 (m, 5H), 3.82 (dd, J=11.1, 5.6 Hz, 3H), 3.51-3.37 (m, 1H), 3.37-2.95 (m, 2H), 2.76 (ddd, J=15.1, 10.0, 5.3 Hz, 2H), 2.62 (ddd, J=13.6, 9.8, 6.5 Hz, 2H), 2.01 (ddd, J=14.4, 5.9, 2.8 Hz, 1H), 1.78 (dddd, J=14.1, 10.4, 6.4, 4.1 Hz, 1H), 1.59 (ddd, J=15.0, 9.0, 6.6 Hz, 1H);  13 C NMR (101 MHz, CD 3 OD) δ 142.25, 128.00, 127.89, 125.26, 78.95, 78.30, 74.37, 70.02, 69.49, 68.71, 39.19, 38.42, 31.36. HR-MS (ESI + , m/z): Calcd for C 15 H 22 O 5  [M+H] +  283.15455 Found 283.15347. 
     3a′ R f =0.49 (silica gel, 8:1 DCM:MeOH, developed with CAM);  1 H NMR (400 MHz, CD 3 OD) 7.22 (t, J=7.5 Hz, 2H), 7.17 (d, J=6.7 Hz, 2H), 7.14-7.07 (m, 1H), 3.87-3.70 (m, 2H), 3.43 (ddd, J=11.0, 9.0, 5.4 Hz, 1H), 3.38-3.20 (m, 2H), 3.12 (t, J=10.9 Hz, 1H), 3.00 (t, J=9.1 Hz, 1H), 2.80-2.54 (m, 2H), 1.92 (ddd, J=14.8, 9.9, 2.3 Hz, 1H), 1.76-1.66 (m, 2H), 1.45 (ddd, J=14.7, 9.6, 2.5 Hz, 1H);  13 C NMR (101 MHz, CD 3 OD) 142.25, 127.99, 127.87, 125.24, 78.49, 77.21, 74.33, 70.21, 69.48, 66.67, 39.73, 39.67, 31.65. HR-MS (ESI + , m/z): Calcd for C 15 H 22 O 5  [M+H] +  283.15455 Found 283.15411. 
     
       
         
         
             
             
         
       
     
     3b and 3b′ were synthesized following general procedure C with 2b (146.2 mg, 0.5 mmol, 1 equiv.), Cu-PMO (16.5 mg, 11 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL) at reflux for 5 hours. The crude mixture containing only 3b and 3b′ was fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show quantitative yield. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3b and 3b′ as clear oils in 17.6% and 4.5%, respectively. 
     Mixture HR-MS (ESI + , m/z): Calcd for C 16 H 25 O 5  [M+H] +  297.17020 Found 297.16939. 
     3b R f =0.32 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.05 (dqd, J=19.4, 8.0, 7.2, 3.8 Hz, 4H), 3.84 (td, J=11.3, 5.9 Hz, 2H), 3.43 (ddd, J=10.5, 8.8, 5.3 Hz, 1H), 3.27-3.16 (m, 2H), 3.15-2.99 (m, 2H), 2.76 (ddd, J=14.0, 10.6, 5.2 Hz, 1H), 2.61 (ddd, J=13.8, 10.5, 6.0 Hz, 1H), 2.37-2.30 (m, 1H), 2.28 (s, 3H), 2.02 (ddd, J=14.4, 6.0, 2.8 Hz, 1H), 1.72 (tdd, J=14.9, 7.2, 4.1 Hz, 1H), 1.61 (ddt, J=17.9, 9.4, 6.5 Hz, 2H).  13 C NMR (101 MHz, CD 3 OD) δ 140.28, 135.40, 129.62, 128.39, 125.51, 125.41, 78.94, 78.29, 74.37, 70.02, 69.51, 69.01, 39.14, 37.09, 28.72, 17.95. HR-MS (ESI + , m/z): Calcd for C 16 H 23 O 5 Na [M+Na] +  319.15214 Found 319.13670. 
     3b′ R f =0.23 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.12-6.99 (m, 4H), 3.82 (dddd, J=14.6, 9.1, 6.6, 3.6 Hz, 2H), 3.44 (dddd, J=12.7, 7.7, 5.4, 2.3 Hz, 1H), 3.38-3.06 (m, 4H), 3.05-2.97 (m, 1H), 2.75 (dt, J=13.7, 8.2 Hz, 1H), 2.61 (dt, J=13.6, 8.0 Hz, 1H), 2.31 (d, J=2.7 Hz, 1H), 2.28 (s, 3H), 2.00-1.87 (m, 1H), 1.70-1.58 (m, 2H), 1.47 (ddd, J=14.4, 9.7, 2.6 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 140.26, 135.38, 129.64, 128.43, 125.53, 125.43, 78.44, 77.17, 74.32, 70.20, 69.48, 66.98, 39.63, 38.47, 29.01, 17.97. HR-MS (ESI + , m/z): Calcd for C 16 H 24 O 5  [M+H] +  297.17020 Found 297.17004. 
     
       
         
         
             
             
         
       
     
     3c and 3c′ were synthesized following general procedure C with 2c (154.2 mg, 0.5 mmol, 1 equiv.), Cu-PMO (16.5 mg, 11 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL) at reflux for 5 hours. The mixture containing only 3c and 3c′ was fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show quantitative yield. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3c and 3c′ as clear oils in 22% and 35% yield, respectively. 
     Mixture HR-MS (ESI + , m/z): Calcd for C 16 H 25 O 6  [M+H] +  313.16511 Found 313.16422. 3c R f =0.41 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.15-7.06 (m, 2H), 6.89-6.84 (m, 1H), 6.81 (td, J=7.4, 1.1 Hz, 1H), 3.85-3.74 (m, 5H), 3.43 (ddd, J=10.6, 8.9, 5.4 Hz, 1H), 3.27-3.14 (m, 2H), 3.06 (dt, J=17.3, 10.0 Hz, 2H), 2.75 (ddd, J=13.5, 10.1, 5.4 Hz, 1H), 2.60 (ddd, J=13.4, 9.9, 6.2 Hz, 1H), 2.01 (ddd, J=14.3, 5.8, 2.9 Hz, 1H), 1.75 (dddd, J=14.2, 10.4, 6.2, 4.4 Hz, 1H), 1.68-1.51 (m, 2H).  13 C NMR (101 MHz, CD 3 OD) δ 157.43, 130.27, 129.40, 126.68, 120.00, 109.94, 79.05, 78.30, 74.38, 70.02, 69.51, 69.14, 54.28, 39.08, 36.61, 25.98. HR-MS (ESI + , m/z): Calcd for C 16 H 24 O 6  [M+H] +  313.16511 Found 313.14989. 
     3c′ R f =0.38 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.16-7.05 (m, 2H), 6.88-6.84 (m, 1H), 6.81 (td, J=7.4, 1.1 Hz, 1H), 3.86-3.73 (m, 5H), 3.44 (ddd, J=10.6, 8.9, 5.4 Hz, 1H), 3.37-3.20 (m, 2H), 3.13 (t, J=10.8 Hz, 1H), 3.06-2.96 (m, 1H), 2.78-2.66 (m, 1H), 2.60 (dt, J=13.5, 7.7 Hz, 1H), 1.91 (ddd, J=14.5, 10.0, 2.4 Hz, 1H), 1.73-1.60 (m, 2H), 1.47 (ddd, J=14.5, 9.7, 2.5 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 157.40, 130.25, 129.40, 126.68, 120.00, 109.94, 78.48, 77.21, 74.36, 70.21, 69.47, 67.04, 54.28, 39.59, 37.99, 26.24. HR-MS (ESI + , m/z): Calcd for C 16 H 24 O 6  [M+H] +  313.16511 Found 313.16446. 
     
       
         
         
             
             
         
       
     
     3d and 3d′ were synthesized following general procedure C with 2d (308.33 mg, 1.0 mmol, 1 equiv.), Cu-PMO (33 mg, 11 mol %) and NaBH 4  (75.6 mg, 2.0 mmol, 2 equiv.) in H 2 O (20 mL) at reflux for 5 hours. The crude mixture containing only 3d and 3d′ was fully dissolved in MeOD and an internal standard (CHCl 3 , 80 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show quantitative yield. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3d and 3d′ as clear oils in 14% and 30% yield, respectively. Mixture HR-MS (ESI + , m/z): Calcd for C 16 H 25 O 6  [M+H] +  313.16511 Found 313.16428. 
     3d R f =0.55 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.11-7.06 (m, 2H), 6.82-6.76 (m, 2H), 3.80 (ddd, J=13.7, 10.3, 4.3 Hz, 2H), 3.73 (s, 3H), 3.42 (ddd, J=10.5, 9.0, 5.4 Hz, 1H), 3.25-3.15 (m, 2H), 3.10 (d, J=10.9 Hz, 1H), 3.08-2.98 (m, 1H), 2.69 (ddd, J=13.7, 10.0, 5.3 Hz, 1H), 2.56 (ddd, J=13.7, 9.8, 6.5 Hz, 1H), 1.99 (ddd, J=14.4, 5.9, 2.8 Hz, 1H), 1.81-1.53 (m, 3H).  13 C NMR (101 MHz, CD 3 OD) δ 157.80, 134.18, 128.86, 113.29, 78.94, 78.26, 74.37, 70.01, 69.49, 68.63, 54.18, 39.20, 38.58, 30.42. HR-MS (ESI + , m/z): Calcd for C 16 H 24 O 6  [M+H] +  313.16511 Found 313.16445. 
     3d′ R f =0.45 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.12-7.02 (m, 2H), 6.86-6.73 (m, 2H), 3.88-3.73 (m, 2H), 3.43 (ddd, J=10.5, 8.9, 5.4 Hz, 1H), 3.37-3.21 (m, 3H), 3.12 (t, J=10.8 Hz, 1H), 3.00 (t, J=9.1 Hz, 1H), 2.74-2.63 (m, 1H), 2.56 (dt, J=13.8, 8.2 Hz, 1H), 1.99-1.82 (m, 1H), 1.67 (td, J=8.1, 5.8 Hz, 2H), 1.44 (ddd, J=14.5, 9.7, 2.6 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 157.78, 134.18, 128.88, 113.30, 78.45, 77.15, 74.32, 70.20, 69.47, 66.53, 54.19, 39.94, 39.69, 30.73. HR-MS (ESI + , m/z): Calcd for C 16 H 24 O 6  [M+H] +  313.16511 Found 313.16386. 
     
       
         
         
             
             
         
       
     
     3e and 3e′ were synthesized following general procedure C with 2e (162.2 mg, 0.5 mmol, 1 equiv.), Cu-PMO (16.5 mg, 11 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL) at reflux for 5 hours. The crude mixture containing only 3e and 3e′ was fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show 93% isolated yield. Attempts to separate diastereomers by column chromatography (silica gel, 15:4:1 EtOAc:MeOH:H 2 O), precipitation/recrystallization and preparatory thin layer chromatography (silica gel, 9:1 DCM:MeOH) were unsuccessful. Characterization data reported below is assessed from analysis of a mixture of 3e and 3e′. Mixture HR-MS (ESI + , m/z): Calcd for C 16 H 25 O 7  [M+H] +  329.16003 Found 329.15889. 
     3e R f =0.64 (silica gel, 15:4:1 EtOAc:MeOH:H 2 O);  1 H NMR (400 MHz, CD 3 OD) δ 6.73 (dd, J=3.3, 1.9 Hz, 1H), 6.68 (dd, J=8.0, 1.4 Hz, 1H), 6.60 (dt, J=8.0, 2.0 Hz, 1H), 3.90-3.73 (m, 5H), 3.52-3.39 (m, 1H), 3.31-2.98 (m, 4H), 2.66 (ddt, J=15.2, 10.1, 5.8 Hz, 1H), 2.53 (ddd, J=13.8, 9.0, 6.9 Hz, 1H), 2.01 (ddd, J=14.4, 5.8, 2.7 Hz, 1H), 1.81-1.53 (m, 3H).  13 C NMR (101 MHz, CD 3 OD) δ 147.35, 143.93, 133.84, 120.36, 114.67, 111.74, 78.97, 77.18, 74.32, 70.01, 69.48, 68.71, 66.61, 54.93, 39.19, 38.63, 30.94. 
     3e′ R f =0.64 (silica gel, 15:4:1 EtOAc:MeOH:H 2 O);  1 H NMR (400 MHz, CD 3 OD) δ 6.73 (dd, J=3.3, 1.9 Hz, 1H), 6.68 (dd, J=8.0, 1.4 Hz, 1H), 6.60 (dt, J=8.0, 2.0 Hz, 1H), 3.90-3.73 (m, 5H), 3.52-3.39 (m, 1H), 3.31-2.98 (m, 4H), 2.66 (ddt, J=15.2, 10.1, 5.8 Hz, 1H), 2.53 (ddd, J=13.8, 9.0, 6.9 Hz, 1H), 1.96-1.86 (m, 1H), 1.81-1.53 (m, 2H), 1.47 (ddd, J=14.7, 9.7, 2.5 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 147.34, 143.93, 133.84, 120.36, 114.67, 111.72, 78.45, 78.26, 74.36, 70.20, 69.48, 68.71, 54.95, 39.95, 39.65, 31.25. 
     
       
         
         
             
             
         
       
     
     3f and 3f′ were synthesized following general procedure C with 2f (173.15 mg, 0.5 mmol, 1 equiv.), Cu-PMO (33 mg, 22 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL) at reflux for 5 hours. The crude mixture was fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show 87% isolated yield. Diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3f and 3f′ as clear oils in 44% and 18% yield, respectively. Mixture HR-MS (ESI + , m/z): Calcd for C 16 H 22 F 3 O 5  [M+H] +  351.14193 Found 351.14087 3f R f =0.31 (silica gel, 8:1 DCM:MeOH);  1 H NMR (600 MHz, CD 3 OD) δ δ 7.56-7.53 (m, 2H), 7.41-7.36 (m, 2H), 3.87-3.77 (m, 2H), 3.42 (ddd, J=10.6, 8.9, 5.4 Hz, 1H), 3.26-3.16 (m, 3H), 3.14-3.07 (m, 1H), 3.02 (dt, J=11.9, 9.4 Hz, 1H), 2.86 (ddd, J=14.7, 10.1, 5.0 Hz, 1H), 2.73 (ddd, J=13.7, 10.1, 6.7 Hz, 1H), 2.06-1.95 (m, 1H), 1.88-1.78 (m, 1H), 1.70 (dddd, J=13.6, 10.0, 8.4, 5.1 Hz, 1H), 1.60 (ddd, J=14.3, 9.1, 6.4 Hz, 1H).  13 C NMR (151 MHz, CD 3 OD) δ 147.06, 128.67, 124.78, 124.75, 124.73, 124.70, 78.76, 78.26, 74.37, 70.00, 69.48, 68.36, 39.20, 37.89, 31.15. HR-MS (ESI + , m/z): Calcd for C 16 H 22 F 3 O 5  [M+H] +  351.14193 Found 351.14106. 
     3f′ R f =0.38 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.53 (d, J=8.1 Hz, 2H), 7.37 (d, J=8.0 Hz, 2H), 3.86-3.72 (m, 2H), 3.43 (ddd, J=10.6, 9.0, 5.3 Hz, 1H), 3.37-3.19 (m, 2H), 3.18-3.07 (m, 1H), 3.00 (t, J=9.1 Hz, 1H), 2.91-2.80 (m, 1H), 2.72 (dt, J=13.8, 8.1 Hz, 1H), 1.94 (ddd, J=14.5, 10.0, 2.4 Hz, 1H), 1.80-1.68 (m, 2H), 1.45 (ddd, J=14.4, 9.8, 2.7 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 147.03, 128.68, 124.80, 124.77, 124.73, 124.69, 78.42, 77.09, 74.29, 70.18, 69.46, 66.40, 39.65, 39.24, 31.46. HR-MS (ESI + , m/z): Calcd for C 16 H 22 F 3 O 5  [M+H] +  351.14193 Found 351.14075. 
     
       
         
         
             
             
         
       
     
     3g and 3g′ were synthesized following general procedure C with 2g (173.15 mg, 0.5 mmol, 1 equiv.), Cu-PMO (33 mg, 22 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL) at reflux for 5 hours. The crude mixture containing 3g and 3g′ was fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show 92% yield. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3g′ as a clear oil in 1% yield. Unfortunately, diastereomer 3g could not be isolated separately from 3g′. Further optimization of separation of the diastereomers is required. Mixture HR-MS (ESI + , m/z): Calcd for C 15 H 22 FO 5  [M+1-1] + 301.14513 Found 301.14436. 
     3g′ R f =0.52 (silica gel, 8:1 DCM:MeOH);  1 H NMR (600 MHz, CD 3 OD) δ 7.23 (td, J=7.6, 1.8 Hz, 1H), 7.16 (tdt, J=10.3, 7.0, 3.4 Hz, 1H), 7.05 (td, J=7.5, 1.3 Hz, 1H), 6.99 (ddd, J=9.8, 8.3, 1.2 Hz, 1H), 3.86-3.73 (m, 2H), 3.43 (ddd, J=10.6, 9.0, 5.3 Hz, 1H), 3.35-3.30 (m, 1H), 3.25 (t, J=8.9 Hz, 1H), 3.17-3.07 (m, 1H), 3.04-2.96 (m, 1H), 2.84-2.73 (m, 1H), 2.72-2.63 (m, 1H), 1.98-1.88 (m, 1H), 1.75-1.66 (m, 2H), 1.45 (ddd, J=14.4, 9.8, 2.6 Hz, 1H).  13 C NMR (151 MHz, CD 3 OD) δ 130.45, 130.41, 128.89, 128.79, 127.28, 127.22, 123.74, 123.71, 114.64, 114.49, 78.44, 77.10, 74.32, 70.20, 69.47, 66.65, 39.63, 38.18, 24.93, 24.91. HR-MS (ESI + , m/z): Calcd for C 15 H 22 FO 5  [M+1-1] + 301.14513 Found 301.14439. 
     
       
         
         
             
             
         
       
     
     3h and 3h′ were synthesized following general procedure C with 2h (154.2 mg, 0.5 mmol, 1 equiv.), Cu-PMO (16.5 mg, 11 wt %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL) at reflux for 5 hours. The crude mixture was fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show 92% yield. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3h and 3h′ as clear oils in 11.7% and 36% yield, respectively. Mixture HR-MS (ESI + , m/z): Calcd for C 15 H 25 O 6  [M+H] +  313.16511 Found 313.16428. 
     3h R f =0.22 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.25-7.14 (m, 4H), 7.12 (d, J=7.1 Hz, 1H), 3.90-3.71 (m, 2H), 3.57 (dd, J=11.8, 5.4 Hz, 1H), 3.31-3.15 (m, 4H), 3.06 (t, J=9.0 Hz, 1H), 2.76 (ddd, J=13.6, 10.1, 5.4 Hz, 1H), 2.63 (ddd, J=13.6, 9.8, 6.5 Hz, 1H), 2.09-1.96 (m, 1H), 1.85-1.64 (m, 2H), 1.60 (ddd, J=14.5, 9.2, 7.3 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 142.26, 128.01, 127.89, 125.25, 80.20, 78.51, 78.21, 74.33, 70.48, 69.17, 61.61, 38.93, 38.67, 31.34. HR-MS (ESI + , m/z): Calcd for C 15 H 25 O 6  [M+H] +  313.16511 Found 313.16406. 
     3h′ R f =0.18 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 7.25-7.15 (m, 4H), 7.15-7.07 (m, 1H), 3.93-3.74 (m, 2H), 3.61 (dd, J=11.7, 5.2 Hz, 1H), 3.40 (td, J=9.5, 2.5 Hz, 1H), 3.36-3.18 (m, 3H), 3.04 (t, J=9.1 Hz, 1H), 2.77 (dt, J=13.5, 7.9 Hz, 1H), 2.62 (dt, J=13.6, 8.1 Hz, 1H), 1.93 (ddd, J=14.4, 9.9, 2.5 Hz, 1H), 1.72 (td, J=8.3, 6.4 Hz, 2H), 1.53 (ddd, J=14.4, 9.6, 2.6 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 142.35, 128.00, 127.89, 125.25, 80.05, 78.39, 76.26, 74.30, 70.58, 66.65, 61.68, 39.73, 39.53, 31.78. HR-MS (ESI + , m/z): Calcd for C 15 H 25 O 6  [M+H] +  313.16511 Found 313.16411. 
     
       
         
         
             
             
         
       
     
     3i and 3i′ were synthesized following general procedure C with 2i (136.1 mg, 0.5 mmol), Cu-PMO (16.5 mg, 11 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL, 0.05 M) at reflux for 5 hours. Because the starting material is very hygroscopic, the true added amount of starting material 2i present in a stock solution was verified by NMR using CHCl 3  (0.04 mL, 0.5 mmol) as internal standard. After reaction, the crude mixture fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. After evaporation in vacuo, the product was weighed to show quantitative yield. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3i′ as a clear oil in 8.2% yield. Unfortunately, diastereomer 3i could not be isolated separately from 3i′. Further optimization of separation of the diastereomers is required. Mixture HR-MS (ESI + , m/z): Calcd for C 14 H 28 O 5 Na [M+Na] + 299.18344 Found 299.14731. 
     3i′ R f =0.42 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) 3.84 (dd, J=11.1, 5.4 Hz, 1H), 3.78 (dd, J=7.1, 4.2 Hz, 1H), 3.43 (ddd, J=10.3, 9.0, 5.4 Hz, 1H), 3.27-3.15 (m, 2H), 3.11 (t, J=10.8 Hz, 1H), 3.03 (t, J=9.1 Hz, 1H), 1.96 (ddd, J=14.4, 5.8, 2.8 Hz, 1H), 1.54 (ddd, J=15.1, 9.0, 6.7 Hz, 1H), 1.50-1.23 (m, 12H), 0.89 (t, J=6.9 Hz, 3H).  13 C NMR (151 MHz, CD 3 OD) δ 79.08, 78.28, 74.41, 70.01, 69.52, 69.34, 39.25, 36.35, 31.60, 29.34, 29.00, 25.09, 22.30, 13.01. HR-MS (ESI + , m/z): Calcd for C 14 H 28 O 5 Na [M+Na] + 299.18344 Found 299.16790. 
     
       
         
         
             
             
         
       
     
     3j and 3j′ were synthesized following general procedure C with 2j (122.2 mg, 0.5 mmol, 1 equiv.), Cu-PMO (16.5 mg, 11 mol %) and NaBH 4  (37.8 mg, 1.0 mmol, 2 equiv.) in H 2 O (10 mL, 0.05 M) at reflux for 5 hours. Because the starting material is very hygroscopic, the true added amount of starting material 2j present in a stock solution was verified by NMR using CHCl 3  (0.04 mL, 0.5 mmol) as internal standard. After reaction, the crude mixture fully dissolved in MeOD and an internal standard (CHCl 3 , 40 μL, 1 equiv.) was added to obtain the NMR yield. Boron NMR was measured to verify the absence of boron salts in the crude mixture. The diastereomers were separated by column chromatography (silica gel, DCM:MeOH, 450:50) to afford 3j′ as a clear oil in 10.2% yield. Unfortunately, diastereomer 3j could not be isolated separately from 3j′. Further optimization of separation of the diastereomers is required. Mixture HR-MS (ESI + , m/z): Calcd for C 12 H 25 O 5  [M+H] +  249.17020 Found 249.16894. 
     3j′ R f =0.25 (silica gel, 8:1 DCM:MeOH);  1 H NMR (400 MHz, CD 3 OD) δ 3.82 (dd, J=11.0, 5.4 Hz, 2H), 3.75-3.65 (m, 1H), 3.43 (ddd, J=10.5, 8.9, 5.4 Hz, 2H), 3.35-3.20 (m, 13H), 3.18-3.07 (m, 1H), 3.00 (q, J=9.2, 8.8 Hz, 1H), 1.91-1.78 (m, 1H), 1.57-1.46 (m, 1H), 1.46-1.37 (m, 2H), 1.36-1.22 (m, 2H), 1.23-1.10 (m, 2H), 1.01-0.93 (m, 2H), 0.88 (dd, J=6.6, 2.5 Hz, 7H).  13 C NMR (151 MHz, CD 3 OD) δ 78.46, 77.19, 74.38, 70.21, 69.48, 67.46, 39.63, 35.55, 34.66, 27.84, 21.68, 21.53. HR-MS (ESI + , m/z): Calcd for C 12 H 24 O 5  [M+Na] + 271.15214 Found 271.12140. 
     4. C-Glycosidic Ketones 5a and 5d 
     
       
         
         
             
             
         
       
     
     R f =0.39 (silica gel, 9:1 DCM:MeOH, develop with CAM); Substrate 2a (83.49 mg, 0.30 mmol, 1 equiv.) was added to a 100 mL Parr reactor. Cu-PMO catalyst (10 mg, 0.03 mmol, 0.11 equiv.) was added to the reactor. MeOH (30 mL, 0.01 M) was added to the reactor by syringe. The vessel was closed and pressurized with H 2  (40 bars at room temperature). The vessel was placed on a stand and heated to 100° C. with stirring for a total of 18 hours. Upon completion, the vessel was cooled using tap water and depressurized inside a fumehood. The vessel was opened and the contents were filtered over a glass filter. The filtrate was washed with methanol. The organic fraction was recovered and concentrated in vacuo to provide crude 5a. 
       1 H NMR (400 MHz, CD 3 OD) δ 7.17 (ddt, J=24.6, 16.3, 7.3 Hz, 5H), 3.79 (ddd, J=21.8, 11.3, 5.6 Hz, 1H), 3.54 (td, J=9.4, 2.8 Hz, 1H), 3.41 (td, J=9.7, 5.3 Hz, 1H), 3.33-3.18 (m, 2H), 3.16-2.99 (m, 2H), 2.97 (m, 4H), 2.53 (dd, J=15.8, 9.3 Hz, 1H).  13 C NMR (101 MHz, CD 3 OD) δ 209.28, 141.09, 127.97, 127.91, 125.56, 78.28, 76.81, 73.67, 70.03, 69.55, 45.07, 44.52, 29.02. 
     
       
         
         
             
             
         
       
     
     Substrate 2d (100 mg, 0.324 mmol, 1 equiv.) was added to a 100 mL Parr reactor. Cu-PMO catalyst (10 mg, 0.03 mmol, 0.11 equiv.) was added to the reactor. MeOH (30 mL, 0.01 M) was added to the reactor by syringe. The vessel was closed and pressurized with H 2  (40 bars at room temperature). The vessel was placed on a stand and heated to 100° C. with stirring for a total of 11 hours. Upon completion, the vessel was cooled using tap water and depressurized inside a fumehood. The vessel was opened and the contents were filtered over a glass filter. he filtrate was washed with methanol. The organic fraction was recovered and concentrated in vacuo to provide crude 5d. Column chromatography (silica gel, 45:5 DCM:MeOH) was performed to yield pure 5d in 20% isolated yield as a white powder (20 mg). 
     R f =0.37 (silica gel, 8:1 DCM:MeOH, develop with CAM);  1 H NMR (400 MHz, CD 3 OD) δ 7.09-7.03 (m, 2H), 6.82-6.75 (m, 2H), 3.78 (s, 3H), 3.76 (dd, J=11.1, 5.4 Hz, 1H), 3.54 (td, J=9.4, 2.8 Hz, 1H), 3.40 (ddd, J=10.5, 9.0, 5.4 Hz, 1H), 3.29 (p, J=1.7 Hz, 1H), 3.23 (t, J=8.9 Hz, 1H), 3.10 (d, J=10.9 Hz, 1H), 3.07-2.97 (m, 1H), 2.85-2.72 (m, 4H), 2.51 (dd, J=15.8, 9.3 Hz, 1H);  13 C NMR (101 MHz, CD 3 OD) δ 209.48, 158.00, 133.00, 128.82, 113.36, 78.26, 76.80, 73.65, 70.03, 69.55, 54.18, 45.09, 44.80, 28.19. 
     L. Procedures and Tables for Calculated Geometries 
     The proton and carbon NMR shifts were calculated computationally in methanol and compared with experimental data of the separated isomers in methanol using Smith and Goodman&#39;s CP3 parameter and related probability factor (Bokor, et al., 2017, Chem. Rev. 117:1687-1764). The full procedure for the calculations of the NMR chemical shifts can be found elsewhere herein. Several conformers of each diastereomer were generated using the Tinker 8.2 program (Bisht, et al, 2011, Carbohydr. Res. 346:1191-1201), and the most stable geometries of all conformers were calculated using Gaussian 16. Ground state geometries were optimized in methanol by using the self-consistent reaction field (SCRF) method combined with the polarized continuum (PCM) solvation model (Cavezza &amp; M. Dalko, WO2010063948A2, 2010) with ωB97XD (Cavezza, et al., 2009, Bioorg. Med. Chem. Lett. 19:845-849) and the def2TZVP (Foley, et al, 2011, Green Chem. 13:321-325; Kirschning, et al., 2000, Biorg. Med. Chem. 8:2347-2354) basis set. NMR shielding constants for proton and carbon nuclei were calculated using GIRO method as implemented in Gaussian 16. 
     To obtain the conformers for the two diastereomers of the compound, 3a and 3a′, for the NMR shift calculations, conformational search was performed using Tinker 8.2 program. Initial structures for the conformational search, DA1 and DB1, were obtained from the gas phase optimization of the two diastereomers ( FIG. 7 ). MMFF force field in gas phase with rms gradient cutoff of 1 kcal/mol was used to obtain ten structures for each diastereomer with sufficiently different conformations. For each of the conformers ground state geometries were optimized using ωB97XD/def2TZVP method in methanol, and then energies and GIAO shielding constants were calculated. 
     1. Coordinates for the Optimized Geometries 
     The following geometries were optimized by Gaussian 16 using ωB971M)/def2TZVP method in methanol: 
     
       
         
           
               
               
               
               
               
             
               
                   
               
               
                 # 
                 Atom 
                 X 
                 Y 
                 Z 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 DA1 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 4.28515 
                 0.178973 
                 0.357223 
               
               
                 2 
                 C 
                 5.075972 
                 −0.96701 
                 0.375162 
               
               
                 3 
                 C 
                 6.325913 
                 −0.98155 
                 −0.22697 
               
               
                 4 
                 C 
                 6.807443 
                 0.155907 
                 −0.85984 
               
               
                 5 
                 C 
                 6.029495 
                 1.304995 
                 −0.88435 
               
               
                 6 
                 C 
                 4.78007 
                 1.313288 
                 −0.28102 
               
               
                 7 
                 H 
                 4.707272 
                 −1.85889 
                 0.869883 
               
               
                 8 
                 H 
                 6.926703 
                 −1.88232 
                 −0.19903 
               
               
                 9 
                 H 
                 7.783727 
                 0.147884 
                 −1.32792 
               
               
                 10 
                 H 
                 6.397657 
                 2.199041 
                 −1.37248 
               
               
                 11 
                 H 
                 4.178574 
                 2.21542 
                 −0.30294 
               
               
                 12 
                 C 
                 2.910011 
                 0.17536 
                 0.968693 
               
               
                 13 
                 H 
                 2.885884 
                 −0.50415 
                 1.82223 
               
               
                 14 
                 H 
                 2.67107 
                 1.173379 
                 1.345701 
               
               
                 15 
                 C 
                 1.837998 
                 −0.24542 
                 −0.03736 
               
               
                 16 
                 H 
                 1.851129 
                 0.441547 
                 −0.88811 
               
               
                 17 
                 H 
                 2.076814 
                 −1.2394 
                 −0.43409 
               
               
                 18 
                 C 
                 0.432428 
                 −0.26907 
                 0.550497 
               
               
                 19 
                 H 
                 0.200556 
                 0.712943 
                 0.96417 
               
               
                 20 
                 C 
                 −0.59898 
                 −0.6253 
                 −0.51761 
               
               
                 21 
                 H 
                 −0.46238 
                 0.023065 
                 −1.38708 
               
               
                 22 
                 H 
                 −0.4052 
                 −1.64953 
                 −0.85173 
               
               
                 23 
                 C 
                 −2.04641 
                 −0.56527 
                 −0.0541 
               
               
                 24 
                 H 
                 −2.10677 
                 −0.89674 
                 0.991608 
               
               
                 25 
                 C 
                 −2.67094 
                 0.826803 
                 −0.16433 
               
               
                 26 
                 H 
                 −2.59508 
                 1.150928 
                 −1.21185 
               
               
                 27 
                 C 
                 −4.14111 
                 0.780132 
                 0.215644 
               
               
                 28 
                 H 
                 −4.21453 
                 0.504466 
                 1.277258 
               
               
                 29 
                 C 
                 −4.86978 
                 −0.26956 
                 −0.59887 
               
               
                 30 
                 H 
                 −4.87545 
                 0.043211 
                 −1.64897 
               
               
                 31 
                 C 
                 −4.13 
                 −1.59735 
                 −0.47035 
               
               
                 32 
                 H 
                 −4.19369 
                 −1.94645 
                 0.569585 
               
               
                 33 
                 H 
                 −4.58147 
                 −2.35152 
                 −1.11526 
               
               
                 34 
                 O 
                 −2.78523 
                 −1.46313 
                 −0.87085 
               
               
                 35 
                 O 
                 −1.97225 
                 1.723495 
                 0.673467 
               
               
                 36 
                 H 
                 −2.48268 
                 2.537791 
                 0.70415 
               
               
                 37 
                 O 
                 −4.66667 
                 2.078435 
                 0.018185 
               
               
                 38 
                 H 
                 −5.58933 
                 2.068215 
                 0.284651 
               
               
                 39 
                 O 
                 −6.19071 
                 −0.35308 
                 −0.09734 
               
               
                 40 
                 H 
                 −6.75142 
                 −0.7695 
                 −0.75452 
               
               
                 41 
                 O 
                 0.345962 
                 −1.15666 
                 1.660781 
               
               
                 42 
                 H 
                 0.566246 
                 −2.04145 
                 1.356249 
               
            
           
           
               
            
               
                 DA2 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 4.368153 
                 −0.312942 
                 0.298696 
               
               
                 2 
                 C 
                 5.019186 
                 −0.790124 
                 −0.83608 
               
               
                 3 
                 C 
                 6.268212 
                 −0.307235 
                 −1.198915 
               
               
                 4 
                 C 
                 6.889416 
                 0.666055 
                 −0.428707 
               
               
                 5 
                 C 
                 6.251614 
                 1.150075 
                 0.704874 
               
               
                 6 
                 C 
                 5.002172 
                 0.663665 
                 1.062297 
               
               
                 7 
                 H 
                 4.540729 
                 −1.552386 
                 −1.441159 
               
               
                 8 
                 H 
                 6.759035 
                 −0.694158 
                 −2.08352 
               
               
                 9 
                 H 
                 7.865441 
                 1.042334 
                 −0.708229 
               
               
                 10 
                 H 
                 6.729463 
                 1.906978 
                 1.314719 
               
               
                 11 
                 H 
                 4.510837 
                 1.04535 
                 1.950598 
               
               
                 12 
                 C 
                 2.993453 
                 −0.806392 
                 0.661417 
               
               
                 13 
                 H 
                 2.882455 
                 −1.848479 
                 0.358387 
               
               
                 14 
                 H 
                 2.863475 
                 −0.770195 
                 1.74656 
               
               
                 15 
                 C 
                 1.894011 
                 0.027255 
                 0.00072 
               
               
                 16 
                 H 
                 2.00016 
                 1.071234 
                 0.307813 
               
               
                 17 
                 H 
                 2.014222 
                 −0.002908 
                 −1.08703 
               
               
                 18 
                 C 
                 0.492851 
                 −0.442305 
                 0.352308 
               
               
                 19 
                 H 
                 0.376083 
                 −0.394306 
                 1.446079 
               
               
                 20 
                 C 
                 −0.571848 
                 0.448698 
                 −0.280574 
               
               
                 21 
                 H 
                 −0.346982 
                 1.491156 
                 −0.050095 
               
               
                 22 
                 H 
                 −0.537539 
                 0.33598 
                 −1.368978 
               
               
                 23 
                 C 
                 −1.978684 
                 0.165821 
                 0.209948 
               
               
                 24 
                 H 
                 −2.006552 
                 0.252425 
                 1.306298 
               
               
                 25 
                 C 
                 −3.012114 
                 1.128349 
                 −0.372218 
               
               
                 26 
                 H 
                 −2.969515 
                 1.060722 
                 −1.468104 
               
               
                 27 
                 C 
                 −4.40917 
                 0.738439 
                 0.080366 
               
               
                 28 
                 H 
                 −4.466407 
                 0.871187 
                 1.170159 
               
               
                 29 
                 C 
                 −4.690795 
                 −0.71856 
                 −0.233402 
               
               
                 30 
                 H 
                 −4.716624 
                 −0.844926 
                 −1.321303 
               
               
                 31 
                 C 
                 −3.575672 
                 −1.580572 
                 0.349 
               
               
                 32 
                 H 
                 −3.593746 
                 −1.511958 
                 1.444289 
               
               
                 33 
                 H 
                 −3.704857 
                 −2.623936 
                 0.063588 
               
               
                 34 
                 O 
                 −2.322031 
                 −1.167065 
                 −0.155237 
               
               
                 35 
                 O 
                 −2.694547 
                 2.436124 
                 0.052198 
               
               
                 36 
                 H 
                 −3.434236 
                 3.001993 
                 −0.186213 
               
               
                 37 
                 O 
                 −5.317583 
                 1.611661 
                 −0.55987 
               
               
                 38 
                 H 
                 −6.20261 
                 1.390875 
                 −0.258686 
               
               
                 39 
                 O 
                 −5.945802 
                 −1.036675 
                 0.336077 
               
               
                 40 
                 H 
                 −6.295502 
                 −1.822057 
                 −0.088908 
               
               
                 41 
                 O 
                 0.363592 
                 −1.793427 
                 −0.071302 
               
               
                 42 
                 H 
                 −0.581096 
                 −1.99122 
                 −0.07958 
               
            
           
           
               
            
               
                 DA3 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −4.07347 
                 0.302679 
                 −0.22945 
               
               
                 2 
                 C 
                 −4.43612 
                 −0.39215 
                 −1.37993 
               
               
                 3 
                 C 
                 −5.74147 
                 −0.82184 
                 −1.57179 
               
               
                 4 
                 C 
                 −6.70841 
                 −0.56205 
                 −0.61093 
               
               
                 5 
                 C 
                 −6.35934 
                 0.130067 
                 0.540475 
               
               
                 6 
                 C 
                 −5.05264 
                 0.557001 
                 0.727214 
               
               
                 7 
                 H 
                 −3.686 
                 −0.59694 
                 −2.13586 
               
               
                 8 
                 H 
                 −6.00446 
                 −1.35825 
                 −2.47517 
               
               
                 9 
                 H 
                 −7.72816 
                 −0.89413 
                 −0.75958 
               
               
                 10 
                 H 
                 −7.10755 
                 0.340653 
                 1.294716 
               
               
                 11 
                 H 
                 −4.78723 
                 1.098282 
                 1.628689 
               
               
                 12 
                 C 
                 −2.64613 
                 0.724505 
                 −0.00344 
               
               
                 13 
                 H 
                 −2.17189 
                 0.919527 
                 −0.96739 
               
               
                 14 
                 H 
                 −2.63559 
                 1.662984 
                 0.557504 
               
               
                 15 
                 C 
                 −1.8574 
                 −0.34397 
                 0.759616 
               
               
                 16 
                 H 
                 −2.37079 
                 −0.56274 
                 1.699565 
               
               
                 17 
                 H 
                 −1.85413 
                 −1.27012 
                 0.177417 
               
               
                 18 
                 C 
                 −0.41153 
                 0.024575 
                 1.086858 
               
               
                 19 
                 H 
                 0.035293 
                 −0.82204 
                 1.607258 
               
               
                 20 
                 C 
                 0.417484 
                 0.327461 
                 −0.15942 
               
               
                 21 
                 H 
                 0.225215 
                 −0.43291 
                 −0.92125 
               
               
                 22 
                 H 
                 0.092143 
                 1.283949 
                 −0.57822 
               
               
                 23 
                 C 
                 1.912908 
                 0.437668 
                 0.098639 
               
               
                 24 
                 H 
                 2.077137 
                 0.862979 
                 1.098662 
               
               
                 25 
                 C 
                 2.650019 
                 −0.89943 
                 0.00642 
               
               
                 26 
                 H 
                 2.472084 
                 −1.31559 
                 −0.9952 
               
               
                 27 
                 C 
                 4.145098 
                 −0.69355 
                 0.178892 
               
               
                 28 
                 H 
                 4.327567 
                 −0.32139 
                 1.197037 
               
               
                 29 
                 C 
                 4.656307 
                 0.340798 
                 −0.80367 
               
               
                 30 
                 H 
                 4.556682 
                 −0.0607 
                 −1.81825 
               
               
                 31 
                 C 
                 3.813771 
                 1.605863 
                 −0.67469 
               
               
                 32 
                 H 
                 3.977094 
                 2.047951 
                 0.317861 
               
               
                 33 
                 H 
                 4.102581 
                 2.337377 
                 −1.42948 
               
               
                 34 
                 O 
                 2.447543 
                 1.321903 
                 −0.87599 
               
               
                 35 
                 O 
                 2.152779 
                 −1.77873 
                 0.992969 
               
               
                 36 
                 H 
                 2.736048 
                 −2.54294 
                 1.011176 
               
               
                 37 
                 O 
                 4.764753 
                 −1.9534 
                 0.008254 
               
               
                 38 
                 H 
                 5.708871 
                 −1.83993 
                 0.143253 
               
               
                 39 
                 O 
                 6.01644 
                 0.581737 
                 −0.49513 
               
               
                 40 
                 H 
                 6.444373 
                 0.985694 
                 −1.25235 
               
               
                 41 
                 O 
                 −0.33816 
                 1.096625 
                 2.022955 
               
               
                 42 
                 H 
                 −0.61061 
                 1.907508 
                 1.586305 
               
            
           
           
               
            
               
                 DA4 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 3.726994 
                 0.189311 
                 0.084951 
               
               
                 2 
                 C 
                 3.840012 
                 −0.809781 
                 1.04865 
               
               
                 3 
                 C 
                 4.682777 
                 −1.894881 
                 0.856603 
               
               
                 4 
                 C 
                 5.429378 
                 −1.999387 
                 −0.308911 
               
               
                 5 
                 C 
                 5.325953 
                 −1.010821 
                 −1.277346 
               
               
                 6 
                 C 
                 4.481057 
                 0.072102 
                 −1.07959 
               
               
                 7 
                 H 
                 3.260729 
                 −0.733589 
                 1.962323 
               
               
                 8 
                 H 
                 4.759181 
                 −2.659336 
                 1.620086 
               
               
                 9 
                 H 
                 6.089859 
                 −2.843983 
                 −0.459765 
               
               
                 10 
                 H 
                 5.906848 
                 −1.081304 
                 −2.188786 
               
               
                 11 
                 H 
                 4.40676 
                 0.841764 
                 −1.839984 
               
               
                 12 
                 C 
                 2.775802 
                 1.339155 
                 0.277828 
               
               
                 13 
                 H 
                 2.710095 
                 1.592104 
                 1.337603 
               
               
                 14 
                 H 
                 3.155473 
                 2.222994 
                 −0.241947 
               
               
                 15 
                 C 
                 1.373682 
                 1.017186 
                 −0.2401 
               
               
                 16 
                 H 
                 1.422894 
                 0.799532 
                 −1.311612 
               
               
                 17 
                 H 
                 1.007892 
                 0.111579 
                 0.252084 
               
               
                 18 
                 C 
                 0.380974 
                 2.153923 
                 −0.006329 
               
               
                 19 
                 H 
                 0.823443 
                 3.073768 
                 −0.400071 
               
               
                 20 
                 C 
                 −0.938788 
                 1.966033 
                 −0.761552 
               
               
                 21 
                 H 
                 −1.624506 
                 2.762396 
                 −0.459782 
               
               
                 22 
                 H 
                 −0.731731 
                 2.111046 
                 −1.824627 
               
               
                 23 
                 C 
                 −1.6697 
                 0.630667 
                 −0.663827 
               
               
                 24 
                 H 
                 −0.987812 
                 −0.194205 
                 −0.913602 
               
               
                 25 
                 C 
                 −2.312074 
                 0.325617 
                 0.692432 
               
               
                 26 
                 H 
                 −2.9515 
                 1.172421 
                 0.972905 
               
               
                 27 
                 C 
                 −3.16423 
                 −0.929344 
                 0.618107 
               
               
                 28 
                 H 
                 −2.499682 
                 −1.781856 
                 0.41835 
               
               
                 29 
                 C 
                 −4.166771 
                 −0.84142 
                 −0.513228 
               
               
                 30 
                 H 
                 −4.886216 
                 −0.046205 
                 −0.28891 
               
               
                 31 
                 C 
                 −3.41839 
                 −0.501183 
                 −1.796827 
               
               
                 32 
                 H 
                 −2.748689 
                 −1.332115 
                 −2.057313 
               
               
                 33 
                 H 
                 −4.116154 
                 −0.349083 
                 −2.620202 
               
               
                 34 
                 O 
                 −2.694673 
                 0.698556 
                 −1.644944 
               
               
                 35 
                 O 
                 −1.298919 
                 0.139736 
                 1.668187 
               
               
                 36 
                 H 
                 −1.721688 
                 −0.203482 
                 2.461692 
               
               
                 37 
                 O 
                 −3.778208 
                 −1.083821 
                 1.88238 
               
               
                 38 
                 H 
                 −4.275426 
                 −1.905452 
                 1.873698 
               
               
                 39 
                 O 
                 −4.816604 
                 −2.095019 
                 −0.596894 
               
               
                 40 
                 H 
                 −5.633537 
                 −1.994379 
                 −1.089057 
               
               
                 41 
                 O 
                 0.191676 
                 2.409887 
                 1.375419 
               
               
                 42 
                 H 
                 −0.272455 
                 1.639624 
                 1.738557 
               
            
           
           
               
            
               
                 DA5 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −3.737352 
                 −0.050669 
                 0.305211 
               
               
                 2 
                 C 
                 −4.613741 
                 0.370725 
                 −0.691266 
               
               
                 3 
                 C 
                 −5.481804 
                 −0.522408 
                 −1.302917 
               
               
                 4 
                 C 
                 −5.487144 
                 −1.857909 
                 −0.925514 
               
               
                 5 
                 C 
                 −4.618878 
                 −2.290846 
                 0.067022 
               
               
                 6 
                 C 
                 −3.752612 
                 −1.393323 
                 0.674357 
               
               
                 7 
                 H 
                 −4.616921 
                 1.413378 
                 −0.989497 
               
               
                 8 
                 H 
                 −6.157972 
                 −0.173819 
                 −2.073882 
               
               
                 9 
                 H 
                 −6.16573 
                 −2.556056 
                 −1.399202 
               
               
                 10 
                 H 
                 −4.617915 
                 −3.330297 
                 0.371422 
               
               
                 11 
                 H 
                 −3.077993 
                 −1.738452 
                 1.450242 
               
               
                 12 
                 C 
                 −2.763582 
                 0.910316 
                 0.932133 
               
               
                 13 
                 H 
                 −3.192805 
                 1.913028 
                 0.953511 
               
               
                 14 
                 H 
                 −2.575154 
                 0.619792 
                 1.969261 
               
               
                 15 
                 C 
                 −1.432981 
                 0.945993 
                 0.178654 
               
               
                 16 
                 H 
                 −1.019142 
                 −0.06513 
                 0.151206 
               
               
                 17 
                 H 
                 −1.605042 
                 1.243501 
                 −0.862627 
               
               
                 18 
                 C 
                 −0.410626 
                 1.884494 
                 0.807081 
               
               
                 19 
                 H 
                 −0.234408 
                 1.569514 
                 1.837484 
               
               
                 20 
                 C 
                 0.922126 
                 1.909558 
                 0.061192 
               
               
                 21 
                 H 
                 0.758343 
                 2.281249 
                 −0.953937 
               
               
                 22 
                 H 
                 1.581239 
                 2.620971 
                 0.566203 
               
               
                 23 
                 C 
                 1.628196 
                 0.571646 
                 −0.035798 
               
               
                 24 
                 H 
                 1.015911 
                 −0.137801 
                 −0.610929 
               
               
                 25 
                 C 
                 2.982818 
                 0.683212 
                 −0.736171 
               
               
                 26 
                 H 
                 3.599427 
                 1.40682 
                 −0.185162 
               
               
                 27 
                 C 
                 3.691137 
                 −0.6604 
                 −0.723064 
               
               
                 28 
                 H 
                 3.104172 
                 −1.364383 
                 −1.330171 
               
               
                 29 
                 C 
                 3.773023 
                 −1.208715 
                 0.688109 
               
               
                 30 
                 H 
                 4.42468 
                 −0.55718 
                 1.280858 
               
               
                 31 
                 C 
                 2.376122 
                 −1.219175 
                 1.301413 
               
               
                 32 
                 H 
                 1.744362 
                 −1.929835 
                 0.751023 
               
               
                 33 
                 H 
                 2.417667 
                 −1.530794 
                 2.345024 
               
               
                 34 
                 O 
                 1.811323 
                 0.072542 
                 1.277562 
               
               
                 35 
                 O 
                 2.771452 
                 1.126026 
                 −2.059902 
               
               
                 36 
                 H 
                 3.605085 
                 1.032127 
                 −2.529387 
               
               
                 37 
                 O 
                 4.966578 
                 −0.471592 
                 −1.303502 
               
               
                 38 
                 H 
                 5.413946 
                 −1.321539 
                 −1.316543 
               
               
                 39 
                 O 
                 4.317454 
                 −2.512142 
                 0.601536 
               
               
                 40 
                 H 
                 4.657006 
                 −2.769588 
                 1.460651 
               
               
                 41 
                 O 
                 −0.917473 
                 3.210426 
                 0.919003 
               
               
                 42 
                 H 
                 −1.101648 
                 3.537406 
                 0.034214 
               
            
           
           
               
            
               
                 DA6 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 4.077917 
                 0.254556 
                 0.337274 
               
               
                 2 
                 C 
                 5.015965 
                 −0.567662 
                 0.955943 
               
               
                 3 
                 C 
                 6.363849 
                 −0.474209 
                 0.641256 
               
               
                 4 
                 C 
                 6.79653 
                 0.446957 
                 −0.302596 
               
               
                 5 
                 C 
                 5.871469 
                 1.272183 
                 −0.926261 
               
               
                 6 
                 C 
                 4.524544 
                 1.174476 
                 −0.60721 
               
               
                 7 
                 H 
                 4.685103 
                 −1.288457 
                 1.695574 
               
               
                 8 
                 H 
                 7.078464 
                 −1.120244 
                 1.136231 
               
               
                 9 
                 H 
                 7.8483 
                 0.523229 
                 −0.548031 
               
               
                 10 
                 H 
                 6.199456 
                 1.996501 
                 −1.661658 
               
               
                 11 
                 H 
                 3.80744 
                 1.824063 
                 −1.096888 
               
               
                 12 
                 C 
                 2.610956 
                 0.119133 
                 0.647976 
               
               
                 13 
                 H 
                 2.482241 
                 −0.161984 
                 1.696633 
               
               
                 14 
                 H 
                 2.126681 
                 1.088854 
                 0.516086 
               
               
                 15 
                 C 
                 1.938482 
                 −0.93101 
                 −0.238188 
               
               
                 16 
                 H 
                 2.034366 
                 −0.64631 
                 −1.290747 
               
               
                 17 
                 H 
                 2.46181 
                 −1.883243 
                 −0.118075 
               
               
                 18 
                 C 
                 0.470712 
                 −1.170149 
                 0.0819 
               
               
                 19 
                 H 
                 0.375399 
                 −1.333024 
                 1.166328 
               
               
                 20 
                 C 
                 −0.418863 
                 0.007641 
                 −0.304816 
               
               
                 21 
                 H 
                 −0.011989 
                 0.926814 
                 0.117562 
               
               
                 22 
                 H 
                 −0.416032 
                 0.116141 
                 −1.394308 
               
               
                 23 
                 C 
                 −1.848239 
                 −0.114627 
                 0.186435 
               
               
                 24 
                 H 
                 −1.847704 
                 −0.252182 
                 1.277887 
               
               
                 25 
                 C 
                 −2.690676 
                 1.117167 
                 −0.140093 
               
               
                 26 
                 H 
                 −2.672246 
                 1.270504 
                 −1.227973 
               
               
                 27 
                 C 
                 −4.131265 
                 0.900145 
                 0.291184 
               
               
                 28 
                 H 
                 −4.15208 
                 0.812648 
                 1.386891 
               
               
                 29 
                 C 
                 −4.681786 
                 −0.385527 
                 −0.295914 
               
               
                 30 
                 H 
                 −4.740245 
                 −0.277906 
                 −1.384532 
               
               
                 31 
                 C 
                 −3.741047 
                 −1.535546 
                 0.048095 
               
               
                 32 
                 H 
                 −3.735653 
                 −1.692003 
                 1.13443 
               
               
                 33 
                 H 
                 −4.064296 
                 −2.457259 
                 −0.434291 
               
               
                 34 
                 O 
                 −2.437244 
                 −1.25943 
                 −0.42187 
               
               
                 35 
                 O 
                 −2.131228 
                 2.230472 
                 0.522507 
               
               
                 36 
                 H 
                 −2.754135 
                 2.957615 
                 0.436378 
               
               
                 37 
                 O 
                 −4.867611 
                 2.035688 
                 −0.115921 
               
               
                 38 
                 H 
                 −5.776291 
                 1.918212 
                 0.17262 
               
               
                 39 
                 O 
                 −5.969073 
                 −0.582715 
                 0.256083 
               
               
                 40 
                 H 
                 −6.465597 
                 −1.181132 
                 −0.305236 
               
               
                 41 
                 O 
                 0.088024 
                 −2.355404 
                 −0.604474 
               
               
                 42 
                 H 
                 −0.877226 
                 −2.370875 
                 −0.615389 
               
            
           
           
               
            
               
                 DA7 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −4.038816 
                 −0.059869 
                 −0.369022 
               
               
                 2 
                 C 
                 −4.538426 
                 −1.340479 
                 −0.147702 
               
               
                 3 
                 C 
                 −5.90142 
                 −1.561278 
                 −0.009362 
               
               
                 4 
                 C 
                 −6.790733 
                 −0.498992 
                 −0.090065 
               
               
                 5 
                 C 
                 −6.305699 
                 0.782736 
                 −0.310616 
               
               
                 6 
                 C 
                 −4.941926 
                 0.997327 
                 −0.447767 
               
               
                 7 
                 H 
                 −3.849589 
                 −2.175853 
                 −0.08579 
               
               
                 8 
                 H 
                 −6.269916 
                 −2.565777 
                 0.158923 
               
               
                 9 
                 H 
                 −7.854863 
                 −0.669072 
                 0.01488 
               
               
                 10 
                 H 
                 −6.991784 
                 1.618061 
                 −0.378872 
               
               
                 11 
                 H 
                 −4.570108 
                 2.001205 
                 −0.621165 
               
               
                 12 
                 C 
                 −2.557124 
                 0.182743 
                 −0.471826 
               
               
                 13 
                 H 
                 −2.077732 
                 −0.699107 
                 −0.901998 
               
               
                 14 
                 H 
                 −2.363243 
                 1.018334 
                 −1.146694 
               
               
                 15 
                 C 
                 −1.939639 
                 0.492454 
                 0.894873 
               
               
                 16 
                 H 
                 −2.483484 
                 1.323489 
                 1.352555 
               
               
                 17 
                 H 
                 −2.065571 
                 −0.369426 
                 1.556006 
               
               
                 18 
                 C 
                 −0.463782 
                 0.863705 
                 0.858084 
               
               
                 19 
                 H 
                 −0.135519 
                 0.995584 
                 1.899345 
               
               
                 20 
                 C 
                 0.412323 
                 −0.215979 
                 0.226804 
               
               
                 21 
                 H 
                 0.148994 
                 −1.185362 
                 0.653586 
               
               
                 22 
                 H 
                 0.222501 
                 −0.265686 
                 −0.849147 
               
               
                 23 
                 C 
                 1.895485 
                 0.001882 
                 0.45439 
               
               
                 24 
                 H 
                 2.092558 
                 0.077097 
                 1.534071 
               
               
                 25 
                 C 
                 2.752137 
                 −1.129447 
                 −0.110924 
               
               
                 26 
                 H 
                 2.536453 
                 −1.224122 
                 −1.184168 
               
               
                 27 
                 C 
                 4.227659 
                 −0.808072 
                 0.056282 
               
               
                 28 
                 H 
                 4.453567 
                 −0.77939 
                 1.131819 
               
               
                 29 
                 C 
                 4.552055 
                 0.552259 
                 −0.530917 
               
               
                 30 
                 H 
                 4.406049 
                 0.510484 
                 −1.615852 
               
               
                 31 
                 C 
                 3.610055 
                 1.592469 
                 0.065951 
               
               
                 32 
                 H 
                 3.80378 
                 1.686999 
                 1.14221 
               
               
                 33 
                 H 
                 3.762194 
                 2.564795 
                 −0.401191 
               
               
                 34 
                 O 
                 2.265189 
                 1.22773 
                 −0.168319 
               
               
                 35 
                 O 
                 2.418342 
                 −2.322589 
                 0.564664 
               
               
                 36 
                 H 
                 3.066208 
                 −2.986113 
                 0.311446 
               
               
                 37 
                 O 
                 4.957935 
                 −1.848267 
                 −0.561995 
               
               
                 38 
                 H 
                 5.893205 
                 −1.665267 
                 −0.441185 
               
               
                 39 
                 O 
                 5.902839 
                 0.833477 
                 −0.21923 
               
               
                 40 
                 H 
                 6.232392 
                 1.505019 
                 −0.819301 
               
               
                 41 
                 O 
                 −0.342219 
                 2.104504 
                 0.173786 
               
               
                 42 
                 H 
                 0.594331 
                 2.216504 
                 −0.02983 
               
            
           
           
               
            
               
                 DA8 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 4.014283 
                 −0.502404 
                 −0.331745 
               
               
                 2 
                 C 
                 4.313913 
                 0.567672 
                 −1.167505 
               
               
                 3 
                 C 
                 5.115965 
                 1.613841 
                 −0.731923 
               
               
                 4 
                 C 
                 5.635818 
                 1.604591 
                 0.55385 
               
               
                 5 
                 C 
                 5.350759 
                 0.537873 
                 1.396357 
               
               
                 6 
                 C 
                 4.550893 
                 −0.504289 
                 0.954009 
               
               
                 7 
                 H 
                 3.907087 
                 0.586667 
                 −2.172231 
               
               
                 8 
                 H 
                 5.333482 
                 2.438826 
                 −1.399351 
               
               
                 9 
                 H 
                 6.260954 
                 2.419472 
                 0.896785 
               
               
                 10 
                 H 
                 5.756212 
                 0.516673 
                 2.400598 
               
               
                 11 
                 H 
                 4.338852 
                 −1.33397 
                 1.619459 
               
               
                 12 
                 C 
                 3.156295 
                 −1.648668 
                 −0.805056 
               
               
                 13 
                 H 
                 2.940494 
                 −1.523908 
                 −1.869382 
               
               
                 14 
                 H 
                 3.739346 
                 −2.569587 
                 −0.715783 
               
               
                 15 
                 C 
                 1.837814 
                 −1.858449 
                 −0.051535 
               
               
                 16 
                 H 
                 1.459271 
                 −2.849713 
                 −0.311981 
               
               
                 17 
                 H 
                 2.013944 
                 −1.860938 
                 1.028369 
               
               
                 18 
                 C 
                 0.741163 
                 −0.853091 
                 −0.366471 
               
               
                 19 
                 H 
                 0.618882 
                 −0.811982 
                 −1.46026 
               
               
                 20 
                 C 
                 −0.593202 
                 −1.279142 
                 0.242878 
               
               
                 21 
                 H 
                 −0.796106 
                 −2.316433 
                 −0.027266 
               
               
                 22 
                 H 
                 −0.524755 
                 −1.228873 
                 1.334406 
               
               
                 23 
                 C 
                 −1.77435 
                 −0.450957 
                 −0.225672 
               
               
                 24 
                 H 
                 −1.82549 
                 −0.479827 
                 −1.324336 
               
               
                 25 
                 C 
                 −3.105366 
                 −0.956085 
                 0.328686 
               
               
                 26 
                 H 
                 −3.047825 
                 −0.949435 
                 1.425969 
               
               
                 27 
                 C 
                 −4.23745 
                 −0.037721 
                 −0.099456 
               
               
                 28 
                 H 
                 −4.334067 
                 −0.098633 
                 −1.192819 
               
               
                 29 
                 C 
                 −3.932646 
                 1.401765 
                 0.26812 
               
               
                 30 
                 H 
                 −3.91523 
                 1.489385 
                 1.359947 
               
               
                 31 
                 C 
                 −2.565815 
                 1.782663 
                 −0.290799 
               
               
                 32 
                 H 
                 −2.600733 
                 1.765213 
                 −1.387699 
               
               
                 33 
                 H 
                 −2.281274 
                 2.783496 
                 0.032464 
               
               
                 34 
                 O 
                 −1.575688 
                 0.896468 
                 0.190062 
               
               
                 35 
                 O 
                 −3.318759 
                 −2.268276 
                 −0.144496 
               
               
                 36 
                 H 
                 −4.221954 
                 −2.509891 
                 0.079223 
               
               
                 37 
                 O 
                 −5.418597 
                 −0.510851 
                 0.515872 
               
               
                 38 
                 H 
                 −6.144888 
                 0.050396 
                 0.23254 
               
               
                 39 
                 O 
                 −4.961368 
                 2.202552 
                 −0.280724 
               
               
                 40 
                 H 
                 −4.984491 
                 3.044737 
                 0.177297 
               
               
                 41 
                 O 
                 1.138829 
                 0.425038 
                 0.108008 
               
               
                 42 
                 H 
                 0.34451 
                 0.973273 
                 0.121838 
               
            
           
           
               
            
               
                 DA9 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −4.038655 
                 −0.059964 
                 −0.368915 
               
               
                 2 
                 C 
                 −4.538256 
                 −1.340407 
                 −0.146557 
               
               
                 3 
                 C 
                 −5.901267 
                 −1.561176 
                 −0.008444 
               
               
                 4 
                 C 
                 −6.790632 
                 −0.499015 
                 −0.090391 
               
               
                 5 
                 C 
                 −6.305609 
                 0.782541 
                 −0.311896 
               
               
                 6 
                 C 
                 −4.941796 
                 0.9971 
                 −0.448831 
               
               
                 7 
                 H 
                 −3.849376 
                 −2.175673 
                 −0.083635 
               
               
                 8 
                 H 
                 −6.269751 
                 −2.565548 
                 0.160626 
               
               
                 9 
                 H 
                 −7.854783 
                 −0.669091 
                 0.014353 
               
               
                 10 
                 H 
                 −6.991708 
                 1.617777 
                 −0.381081 
               
               
                 11 
                 H 
                 −4.570013 
                 2.000862 
                 −0.622967 
               
               
                 12 
                 C 
                 −2.556935 
                 0.182542 
                 −0.471542 
               
               
                 13 
                 H 
                 −2.07754 
                 −0.699589 
                 −0.901158 
               
               
                 14 
                 H 
                 −2.362919 
                 1.017746 
                 −1.146859 
               
               
                 15 
                 C 
                 −1.939635 
                 0.492907 
                 0.895033 
               
               
                 16 
                 H 
                 −2.483442 
                 1.324196 
                 1.352307 
               
               
                 17 
                 H 
                 −2.065684 
                 −0.368656 
                 1.556554 
               
               
                 18 
                 C 
                 −0.463726 
                 0.864006 
                 0.858281 
               
               
                 19 
                 H 
                 −0.135493 
                 0.995921 
                 1.899541 
               
               
                 20 
                 C 
                 0.412248 
                 −0.215731 
                 0.226928 
               
               
                 21 
                 H 
                 0.148806 
                 −1.18516 
                 0.653524 
               
               
                 22 
                 H 
                 0.222395 
                 −0.265187 
                 −0.849042 
               
               
                 23 
                 C 
                 1.895431 
                 0.00191 
                 0.454547 
               
               
                 24 
                 H 
                 2.092512 
                 0.076875 
                 1.534243 
               
               
                 25 
                 C 
                 2.751915 
                 −1.129416 
                 −0.111012 
               
               
                 26 
                 H 
                 2.536063 
                 −1.223974 
                 −1.184228 
               
               
                 27 
                 C 
                 4.227521 
                 −0.808268 
                 0.055969 
               
               
                 28 
                 H 
                 4.45368 
                 −0.779976 
                 1.131452 
               
               
                 29 
                 C 
                 4.551992 
                 0.55219 
                 −0.530887 
               
               
                 30 
                 H 
                 4.405836 
                 0.510716 
                 −1.615817 
               
               
                 31 
                 C 
                 3.610177 
                 1.592339 
                 0.066369 
               
               
                 32 
                 H 
                 3.803994 
                 1.686543 
                 1.142643 
               
               
                 33 
                 H 
                 3.762397 
                 2.564791 
                 −0.40049 
               
               
                 34 
                 O 
                 2.265244 
                 1.227847 
                 −0.16789 
               
               
                 35 
                 O 
                 2.4181 
                 −2.32259 
                 0.564535 
               
               
                 36 
                 H 
                 3.065281 
                 −2.986423 
                 0.310384 
               
               
                 37 
                 O 
                 4.957478 
                 −1.848408 
                 −0.562831 
               
               
                 38 
                 H 
                 5.892807 
                 −1.66605 
                 −0.441552 
               
               
                 39 
                 O 
                 5.902838 
                 0.833191 
                 −0.219299 
               
               
                 40 
                 H 
                 6.232122 
                 1.505498 
                 −0.818667 
               
               
                 41 
                 O 
                 −0.341959 
                 2.104792 
                 0.173975 
               
               
                 42 
                 H 
                 0.594555 
                 2.216409 
                 −0.02997 
               
            
           
           
               
            
               
                 DA10 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −3.233047 
                 0.071892 
                 0.440079 
               
               
                 2 
                 C 
                 −4.554639 
                 0.485668 
                 0.305698 
               
               
                 3 
                 C 
                 −5.545422 
                 −0.407221 
                 −0.079926 
               
               
                 4 
                 C 
                 −5.226583 
                 −1.732343 
                 −0.339135 
               
               
                 5 
                 C 
                 −3.910967 
                 −2.157328 
                 −0.209087 
               
               
                 6 
                 C 
                 −2.925734 
                 −1.261149 
                 0.176622 
               
               
                 7 
                 H 
                 −4.811512 
                 1.519621 
                 0.507912 
               
               
                 8 
                 H 
                 −6.569168 
                 −0.066815 
                 −0.175909 
               
               
                 9 
                 H 
                 −5.998261 
                 −2.430608 
                 −0.63797 
               
               
                 10 
                 H 
                 −3.652729 
                 −3.190539 
                 −0.406562 
               
               
                 11 
                 H 
                 −1.898682 
                 −1.593889 
                 0.277594 
               
               
                 12 
                 C 
                 −2.143215 
                 1.039791 
                 0.814053 
               
               
                 13 
                 H 
                 −2.564513 
                 1.869828 
                 1.387171 
               
               
                 14 
                 H 
                 −1.420309 
                 0.532246 
                 1.454142 
               
               
                 15 
                 C 
                 −1.42799 
                 1.584278 
                 −0.422336 
               
               
                 16 
                 H 
                 −1.036053 
                 0.751461 
                 −1.011482 
               
               
                 17 
                 H 
                 −2.148614 
                 2.112609 
                 −1.052162 
               
               
                 18 
                 C 
                 −0.296903 
                 2.547587 
                 −0.100746 
               
               
                 19 
                 H 
                 −0.702966 
                 3.365658 
                 0.508831 
               
               
                 20 
                 C 
                 0.874974 
                 1.94161 
                 0.673384 
               
               
                 21 
                 H 
                 1.635196 
                 2.717794 
                 0.787063 
               
               
                 22 
                 H 
                 0.559326 
                 1.667556 
                 1.68291 
               
               
                 23 
                 C 
                 1.516533 
                 0.73007 
                 0.021373 
               
               
                 24 
                 H 
                 1.483277 
                 0.842178 
                 −1.072081 
               
               
                 25 
                 C 
                 2.978672 
                 0.550493 
                 0.43046 
               
               
                 26 
                 H 
                 3.027006 
                 0.466818 
                 1.525169 
               
               
                 27 
                 C 
                 3.540757 
                 −0.722845 
                 −0.177822 
               
               
                 28 
                 H 
                 3.555808 
                 −0.600325 
                 −1.270281 
               
               
                 29 
                 C 
                 2.661521 
                 −1.913681 
                 0.149893 
               
               
                 30 
                 H 
                 2.70648 
                 −2.097201 
                 1.229187 
               
               
                 31 
                 C 
                 1.223499 
                 −1.594908 
                 −0.247015 
               
               
                 32 
                 H 
                 1.16194 
                 −1.485472 
                 −1.338471 
               
               
                 33 
                 H 
                 0.554941 
                 −2.401032 
                 0.056315 
               
               
                 34 
                 O 
                 0.781824 
                 −0.42405 
                 0.400005 
               
               
                 35 
                 O 
                 3.710433 
                 1.676103 
                 −0.008283 
               
               
                 36 
                 H 
                 4.642609 
                 1.479418 
                 0.119316 
               
               
                 37 
                 O 
                 4.860222 
                 −0.878412 
                 0.307067 
               
               
                 38 
                 H 
                 5.228952 
                 −1.671158 
                 −0.090875 
               
               
                 39 
                 O 
                 3.172885 
                 −3.022732 
                 −0.565568 
               
               
                 40 
                 H 
                 2.847114 
                 −3.832052 
                 −0.167439 
               
               
                 41 
                 O 
                 0.143886 
                 3.071617 
                 −1.350631 
               
               
                 42 
                 H 
                 0.857418 
                 3.692221 
                 −1.186082 
               
            
           
           
               
            
               
                 DB1 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 4.294699 
                 −0.36284 
                 −0.15292 
               
               
                 2 
                 C 
                 4.895617 
                 0.186247 
                 −1.28254 
               
               
                 3 
                 C 
                 6.170219 
                 0.731219 
                 −1.21973 
               
               
                 4 
                 C 
                 6.866828 
                 0.737117 
                 −0.01947 
               
               
                 5 
                 C 
                 6.279069 
                 0.193242 
                 1.114264 
               
               
                 6 
                 C 
                 5.004821 
                 −0.351 
                 1.045036 
               
               
                 7 
                 H 
                 4.358037 
                 0.183531 
                 −2.2244 
               
               
                 8 
                 H 
                 6.621399 
                 1.149809 
                 −2.11097 
               
               
                 9 
                 H 
                 7.86244 
                 1.159566 
                 0.031509 
               
               
                 10 
                 H 
                 6.815985 
                 0.189543 
                 2.054927 
               
               
                 11 
                 H 
                 4.553033 
                 −0.7769 
                 1.934215 
               
               
                 12 
                 C 
                 2.894947 
                 −0.91246 
                 −0.21165 
               
               
                 13 
                 H 
                 2.696493 
                 −1.31106 
                 −1.21025 
               
               
                 14 
                 H 
                 2.793227 
                 −1.74207 
                 0.489655 
               
               
                 15 
                 C 
                 1.847461 
                 0.152383 
                 0.114523 
               
               
                 16 
                 H 
                 2.039343 
                 0.564039 
                 1.113004 
               
               
                 17 
                 H 
                 1.946975 
                 0.983016 
                 −0.58956 
               
               
                 18 
                 C 
                 0.414146 
                 −0.36855 
                 0.054313 
               
               
                 19 
                 C 
                 −0.58096 
                 0.746167 
                 0.379061 
               
               
                 20 
                 H 
                 −0.68523 
                 0.803236 
                 1.467382 
               
               
                 21 
                 H 
                 −0.16639 
                 1.704603 
                 0.059199 
               
               
                 22 
                 C 
                 −1.98187 
                 0.664797 
                 −0.21746 
               
               
                 23 
                 H 
                 −1.93359 
                 0.855648 
                 −1.30005 
               
               
                 24 
                 C 
                 −2.714 
                 −0.66813 
                 −0.0283 
               
               
                 25 
                 H 
                 −2.60845 
                 −0.98729 
                 1.016356 
               
               
                 26 
                 C 
                 −4.19665 
                 −0.54304 
                 −0.35343 
               
               
                 27 
                 H 
                 −4.28749 
                 −0.39189 
                 −1.4387 
               
               
                 28 
                 C 
                 −4.83391 
                 0.647534 
                 0.32772 
               
               
                 29 
                 H 
                 −4.81741 
                 0.496178 
                 1.412821 
               
               
                 30 
                 C 
                 −4.01715 
                 1.883459 
                 −0.02157 
               
               
                 31 
                 H 
                 −4.05831 
                 2.056014 
                 −1.10595 
               
               
                 32 
                 H 
                 −4.41273 
                 2.765261 
                 0.482869 
               
               
                 33 
                 O 
                 −2.68941 
                 1.720822 
                 0.416305 
               
               
                 34 
                 O 
                 −2.13228 
                 −1.617 
                 −0.89935 
               
               
                 35 
                 H 
                 −2.60922 
                 −2.44249 
                 −0.78352 
               
               
                 36 
                 O 
                 −4.80569 
                 −1.7667 
                 0.012099 
               
               
                 37 
                 H 
                 −5.7375 
                 −1.70814 
                 −0.21411 
               
               
                 38 
                 O 
                 −6.16566 
                 0.737194 
                 −0.14432 
               
               
                 39 
                 H 
                 −6.6742 
                 1.289941 
                 0.451998 
               
               
                 40 
                 O 
                 0.239224 
                 −1.48604 
                 0.918934 
               
               
                 41 
                 H 
                 0.451804 
                 −1.20314 
                 1.812449 
               
               
                 42 
                 H 
                 0.2227 
                 −0.76042 
                 −0.94553 
               
            
           
           
               
            
               
                 DB2 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 3.487878 
                 −0.314061 
                 −0.331546 
               
               
                 2 
                 C 
                 3.056219 
                 0.482323 
                 −1.388424 
               
               
                 3 
                 C 
                 3.316421 
                 1.845668 
                 −1.408015 
               
               
                 4 
                 C 
                 4.016799 
                 2.43622 
                 −0.366193 
               
               
                 5 
                 C 
                 4.454811 
                 1.652924 
                 0.693253 
               
               
                 6 
                 C 
                 4.190981 
                 0.291422 
                 0.707614 
               
               
                 7 
                 H 
                 2.50095 
                 0.026522 
                 −2.200066 
               
               
                 8 
                 H 
                 2.971456 
                 2.44761 
                 −2.239758 
               
               
                 9 
                 H 
                 4.222658 
                 3.499127 
                 −0.380098 
               
               
                 10 
                 H 
                 5.006306 
                 2.103612 
                 1.509277 
               
               
                 11 
                 H 
                 4.537547 
                 −0.313903 
                 1.538225 
               
               
                 12 
                 C 
                 3.162985 
                 −1.784222 
                 −0.282235 
               
               
                 13 
                 H 
                 2.96219 
                 −2.150484 
                 −1.289765 
               
               
                 14 
                 H 
                 4.026804 
                 −2.335446 
                 0.095688 
               
               
                 15 
                 C 
                 1.9599 
                 −2.096425 
                 0.615221 
               
               
                 16 
                 H 
                 1.81756 
                 −3.179844 
                 0.663047 
               
               
                 17 
                 H 
                 2.168949 
                 −1.751007 
                 1.631443 
               
               
                 18 
                 C 
                 0.664191 
                 −1.456036 
                 0.146907 
               
               
                 19 
                 C 
                 −0.481923 
                 −1.757482 
                 1.108172 
               
               
                 20 
                 H 
                 −0.664952 
                 −2.835286 
                 1.11682 
               
               
                 21 
                 H 
                 −0.179575 
                 −1.479637 
                 2.120319 
               
               
                 22 
                 C 
                 −1.794812 
                 −1.050545 
                 0.805633 
               
               
                 23 
                 H 
                 −2.533469 
                 −1.352301 
                 1.561107 
               
               
                 24 
                 C 
                 −1.706751 
                 0.48103 
                 0.825726 
               
               
                 25 
                 H 
                 −0.978236 
                 0.817155 
                 0.080175 
               
               
                 26 
                 C 
                 −3.056568 
                 1.080109 
                 0.46758 
               
               
                 27 
                 H 
                 −3.778026 
                 0.798766 
                 1.248064 
               
               
                 28 
                 C 
                 −3.544387 
                 0.52665 
                 −0.85784 
               
               
                 29 
                 H 
                 −2.857659 
                 0.86323 
                 −1.645449 
               
               
                 30 
                 C 
                 −3.53156 
                 −0.992937 
                 −0.808976 
               
               
                 31 
                 H 
                 −4.269535 
                 −1.341847 
                 −0.075381 
               
               
                 32 
                 H 
                 −3.786668 
                 −1.40683 
                 −1.782997 
               
               
                 33 
                 O 
                 −2.247495 
                 −1.47606 
                 −0.475853 
               
               
                 34 
                 O 
                 −1.364669 
                 0.969504 
                 2.109564 
               
               
                 35 
                 H 
                 −0.410458 
                 1.00638 
                 2.195523 
               
               
                 36 
                 O 
                 −2.993585 
                 2.486222 
                 0.352028 
               
               
                 37 
                 H 
                 −2.660831 
                 2.832802 
                 1.184347 
               
               
                 38 
                 O 
                 −4.862788 
                 0.93775 
                 −1.144824 
               
               
                 39 
                 H 
                 −4.892974 
                 1.894973 
                 −1.066067 
               
               
                 40 
                 O 
                 0.388102 
                 −1.928475 
                 −1.165158 
               
               
                 41 
                 H 
                 −0.544715 
                 −1.753799 
                 −1.339787 
               
               
                 42 
                 H 
                 0.82105 
                 −0.369169 
                 0.108021 
               
            
           
           
               
            
               
                 DB3 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −3.767125 
                 −0.316259 
                 0.186337 
               
               
                 2 
                 C 
                 −3.514108 
                 0.90246 
                 0.809928 
               
               
                 3 
                 C 
                 −3.90832 
                 2.098297 
                 0.226311 
               
               
                 4 
                 C 
                 −4.56568 
                 2.094038 
                 −0.995554 
               
               
                 5 
                 C 
                 −4.824887 
                 0.885497 
                 −1.627766 
               
               
                 6 
                 C 
                 −4.42745 
                 −0.306389 
                 −1.040134 
               
               
                 7 
                 H 
                 −2.992705 
                 0.910248 
                 1.759988 
               
               
                 8 
                 H 
                 −3.70138 
                 3.035771 
                 0.727793 
               
               
                 9 
                 H 
                 −4.876072 
                 3.025694 
                 −1.451707 
               
               
                 10 
                 H 
                 −5.340852 
                 0.871083 
                 −2.579997 
               
               
                 11 
                 H 
                 −4.635221 
                 −1.246642 
                 −1.539326 
               
               
                 12 
                 C 
                 −3.300696 
                 −1.61277 
                 0.795178 
               
               
                 13 
                 H 
                 −3.200925 
                 −1.495079 
                 1.875198 
               
               
                 14 
                 H 
                 −4.05218 
                 −2.386327 
                 0.623061 
               
               
                 15 
                 C 
                 −1.966921 
                 −2.095335 
                 0.215657 
               
               
                 16 
                 H 
                 −1.729092 
                 −3.08086 
                 0.632224 
               
               
                 17 
                 H 
                 −2.069508 
                 −2.227516 
                 −0.864988 
               
               
                 18 
                 C 
                 −0.796806 
                 −1.151148 
                 0.478243 
               
               
                 19 
                 C 
                 0.495551 
                 −1.705895 
                 −0.120547 
               
               
                 20 
                 H 
                 0.940658 
                 −2.395918 
                 0.603555 
               
               
                 21 
                 H 
                 0.258611 
                 −2.299308 
                 −1.006363 
               
               
                 22 
                 C 
                 1.574129 
                 −0.714042 
                 −0.542233 
               
               
                 23 
                 H 
                 1.24606 
                 −0.173858 
                 −1.44295 
               
               
                 24 
                 C 
                 1.954979 
                 0.342398 
                 0.500963 
               
               
                 25 
                 H 
                 2.097636 
                 −0.150084 
                 1.471127 
               
               
                 26 
                 C 
                 3.243838 
                 1.06123 
                 0.124667 
               
               
                 27 
                 H 
                 3.031989 
                 1.685077 
                 −0.755535 
               
               
                 28 
                 C 
                 4.346739 
                 0.097842 
                 −0.253624 
               
               
                 29 
                 H 
                 4.625551 
                 −0.49664 
                 0.623645 
               
               
                 30 
                 C 
                 3.813641 
                 −0.825705 
                 −1.339761 
               
               
                 31 
                 H 
                 3.561228 
                 −0.235675 
                 −2.231697 
               
               
                 32 
                 H 
                 4.561008 
                 −1.568857 
                 −1.618501 
               
               
                 33 
                 O 
                 2.691929 
                 −1.529651 
                 −0.862988 
               
               
                 34 
                 O 
                 0.906845 
                 1.288186 
                 0.572427 
               
               
                 35 
                 H 
                 1.162129 
                 1.950827 
                 1.218925 
               
               
                 36 
                 O 
                 3.594951 
                 1.883638 
                 1.221218 
               
               
                 37 
                 H 
                 4.393489 
                 2.361933 
                 0.983652 
               
               
                 38 
                 O 
                 5.443892 
                 0.871926 
                 −0.702557 
               
               
                 39 
                 H 
                 6.236979 
                 0.333 
                 −0.685915 
               
               
                 40 
                 O 
                 −0.652267 
                 −0.892746 
                 1.871352 
               
               
                 41 
                 H 
                 −0.523081 
                 −1.734776 
                 2.316028 
               
               
                 42 
                 H 
                 −1.018433 
                 −0.178236 
                 0.040171 
               
            
           
           
               
            
               
                 DB4 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −2.42523 
                 −0.00765 
                 −0.52919 
               
               
                 2 
                 C 
                 −2.18392 
                 −1.29937 
                 −0.07009 
               
               
                 3 
                 C 
                 −3.2263 
                 −2.11468 
                 0.349953 
               
               
                 4 
                 C 
                 −4.53208 
                 −1.64889 
                 0.315864 
               
               
                 5 
                 C 
                 −4.78701 
                 −0.36325 
                 −0.14313 
               
               
                 6 
                 C 
                 −3.7421 
                 0.446822 
                 −0.56035 
               
               
                 7 
                 H 
                 −1.1684 
                 −1.679 
                 −0.03933 
               
               
                 8 
                 H 
                 −3.01592 
                 −3.11698 
                 0.702286 
               
               
                 9 
                 H 
                 −5.34684 
                 −2.28349 
                 0.640942 
               
               
                 10 
                 H 
                 −5.80378 
                 0.008145 
                 −0.17886 
               
               
                 11 
                 H 
                 −3.94992 
                 1.448388 
                 −0.92065 
               
               
                 12 
                 C 
                 −1.29524 
                 0.894746 
                 −0.94685 
               
               
                 13 
                 H 
                 −0.41026 
                 0.300226 
                 −1.17677 
               
               
                 14 
                 H 
                 −1.56118 
                 1.416217 
                 −1.87027 
               
               
                 15 
                 C 
                 −0.96274 
                 1.944944 
                 0.119949 
               
               
                 16 
                 H 
                 −1.8041 
                 2.63605 
                 0.197489 
               
               
                 17 
                 H 
                 −0.86154 
                 1.474812 
                 1.10154 
               
               
                 18 
                 C 
                 0.281606 
                 2.771235 
                 −0.20827 
               
               
                 19 
                 C 
                 1.569195 
                 2.359984 
                 0.514257 
               
               
                 20 
                 H 
                 2.336398 
                 3.088643 
                 0.236353 
               
               
                 21 
                 H 
                 1.411553 
                 2.459117 
                 1.590208 
               
               
                 22 
                 C 
                 2.150052 
                 0.977345 
                 0.244989 
               
               
                 23 
                 H 
                 3.199281 
                 0.99282 
                 0.576212 
               
               
                 24 
                 C 
                 1.478233 
                 −0.16701 
                 1.010819 
               
               
                 25 
                 H 
                 0.416105 
                 −0.21308 
                 0.758201 
               
               
                 26 
                 C 
                 2.101411 
                 −1.49672 
                 0.623495 
               
               
                 27 
                 H 
                 3.143777 
                 −1.5072 
                 0.97271 
               
               
                 28 
                 C 
                 2.106006 
                 −1.6688 
                 −0.88297 
               
               
                 29 
                 H 
                 1.069402 
                 −1.73762 
                 −1.23352 
               
               
                 30 
                 C 
                 2.773906 
                 −0.45596 
                 −1.52225 
               
               
                 31 
                 H 
                 3.829987 
                 −0.42348 
                 −1.22133 
               
               
                 32 
                 H 
                 2.725908 
                 −0.51966 
                 −2.60922 
               
               
                 33 
                 O 
                 2.110723 
                 0.730559 
                 −1.14898 
               
               
                 34 
                 O 
                 1.633138 
                 0.081609 
                 2.392069 
               
               
                 35 
                 H 
                 1.31463 
                 −0.69365 
                 2.862341 
               
               
                 36 
                 O 
                 1.362493 
                 −2.51085 
                 1.275453 
               
               
                 37 
                 H 
                 1.746106 
                 −3.3578 
                 1.033553 
               
               
                 38 
                 O 
                 2.804662 
                 −2.8655 
                 −1.16616 
               
               
                 39 
                 H 
                 2.579572 
                 −3.16153 
                 −2.0502 
               
               
                 40 
                 O 
                 −0.0213 
                 4.119188 
                 0.155249 
               
               
                 41 
                 H 
                 0.742887 
                 4.666191 
                 −0.04096 
               
               
                 42 
                 H 
                 0.453933 
                 2.726332 
                 −1.28912 
               
            
           
           
               
            
               
                 DB5 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −3.86344 
                 −0.40234 
                 0.060083 
               
               
                 2 
                 C 
                 −3.78529 
                 0.590768 
                 1.03221 
               
               
                 3 
                 C 
                 −4.20972 
                 1.885571 
                 0.767018 
               
               
                 4 
                 C 
                 −4.7217 
                 2.208472 
                 −0.48115 
               
               
                 5 
                 C 
                 −4.80664 
                 1.226959 
                 −1.45962 
               
               
                 6 
                 C 
                 −4.38028 
                 −0.06457 
                 −1.1888 
               
               
                 7 
                 H 
                 −3.38056 
                 0.344923 
                 2.007446 
               
               
                 8 
                 H 
                 −4.14012 
                 2.643394 
                 1.537712 
               
               
                 9 
                 H 
                 −5.05496 
                 3.217219 
                 −0.69021 
               
               
                 10 
                 H 
                 −5.20876 
                 1.467998 
                 −2.43601 
               
               
                 11 
                 H 
                 −4.45129 
                 −0.82578 
                 −1.95815 
               
               
                 12 
                 C 
                 −3.36139 
                 −1.79631 
                 0.331113 
               
               
                 13 
                 H 
                 −3.33684 
                 −1.97353 
                 1.407044 
               
               
                 14 
                 H 
                 −4.05372 
                 −2.5228 
                 −0.10012 
               
               
                 15 
                 C 
                 −1.96674 
                 −2.0537 
                 −0.24954 
               
               
                 16 
                 H 
                 −1.68852 
                 −3.0957 
                 −0.0649 
               
               
                 17 
                 H 
                 −1.99244 
                 −1.91775 
                 −1.33408 
               
               
                 18 
                 C 
                 −0.88302 
                 −1.15347 
                 0.319292 
               
               
                 19 
                 C 
                 0.454202 
                 −1.40109 
                 −0.37176 
               
               
                 20 
                 H 
                 0.729114 
                 −2.4522 
                 −0.25931 
               
               
                 21 
                 H 
                 0.341755 
                 −1.20225 
                 −1.44162 
               
               
                 22 
                 C 
                 1.5879 
                 −0.55028 
                 0.161967 
               
               
                 23 
                 H 
                 1.720945 
                 −0.74697 
                 1.238503 
               
               
                 24 
                 C 
                 2.919963 
                 −0.84119 
                 −0.53879 
               
               
                 25 
                 H 
                 2.78763 
                 −0.70358 
                 −1.61529 
               
               
                 26 
                 C 
                 3.996247 
                 0.120909 
                 −0.05083 
               
               
                 27 
                 H 
                 4.186493 
                 −0.08136 
                 1.014733 
               
               
                 28 
                 C 
                 3.528044 
                 1.557947 
                 −0.17451 
               
               
                 29 
                 H 
                 3.402862 
                 1.790604 
                 −1.23992 
               
               
                 30 
                 C 
                 2.18456 
                 1.707494 
                 0.521903 
               
               
                 31 
                 H 
                 2.310337 
                 1.535456 
                 1.599597 
               
               
                 32 
                 H 
                 1.79291 
                 2.713235 
                 0.376259 
               
               
                 33 
                 O 
                 1.240772 
                 0.811764 
                 −0.01954 
               
               
                 34 
                 O 
                 3.343093 
                 −2.18188 
                 −0.37539 
               
               
                 35 
                 H 
                 3.413537 
                 −2.37402 
                 0.564584 
               
               
                 36 
                 O 
                 5.194865 
                 −0.01314 
                 −0.78646 
               
               
                 37 
                 H 
                 5.45802 
                 −0.93699 
                 −0.75543 
               
               
                 38 
                 O 
                 4.433943 
                 2.459693 
                 0.424092 
               
               
                 39 
                 H 
                 5.303979 
                 2.288131 
                 0.054226 
               
               
                 40 
                 O 
                 −0.79608 
                 −1.40727 
                 1.720273 
               
               
                 41 
                 H 
                 −0.45871 
                 −0.62302 
                 2.155878 
               
               
                 42 
                 H 
                 −1.17054 
                 −0.10936 
                 0.16365 
               
            
           
           
               
            
               
                 DB6 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 3.701258 
                 0.180996 
                 0.357074 
               
               
                 2 
                 C 
                 3.727133 
                 −0.94712 
                 1.173277 
               
               
                 3 
                 C 
                 4.595704 
                 −1.99702 
                 0.912944 
               
               
                 4 
                 C 
                 5.455876 
                 −1.93601 
                 −0.1747 
               
               
                 5 
                 C 
                 5.439828 
                 −0.81775 
                 −0.9964 
               
               
                 6 
                 C 
                 4.569368 
                 0.229704 
                 −0.73036 
               
               
                 7 
                 H 
                 3.058858 
                 −1.00118 
                 2.025735 
               
               
                 8 
                 H 
                 4.602919 
                 −2.86384 
                 1.562305 
               
               
                 9 
                 H 
                 6.136187 
                 −2.75323 
                 −0.3787 
               
               
                 10 
                 H 
                 6.109294 
                 −0.75906 
                 −1.8458 
               
               
                 11 
                 H 
                 4.564136 
                 1.101416 
                 −1.37543 
               
               
                 12 
                 C 
                 2.723785 
                 1.295755 
                 0.615454 
               
               
                 13 
                 H 
                 2.549012 
                 1.38909 
                 1.690919 
               
               
                 14 
                 H 
                 3.143874 
                 2.243807 
                 0.276099 
               
               
                 15 
                 C 
                 1.386565 
                 1.052375 
                 −0.08549 
               
               
                 16 
                 H 
                 1.543915 
                 0.973541 
                 −1.16757 
               
               
                 17 
                 H 
                 0.978156 
                 0.091337 
                 0.233307 
               
               
                 18 
                 C 
                 0.35671 
                 2.139787 
                 0.188619 
               
               
                 19 
                 C 
                 −1.00579 
                 1.873299 
                 −0.4486 
               
               
                 20 
                 H 
                 −1.64394 
                 2.729017 
                 −0.22419 
               
               
                 21 
                 H 
                 −0.90397 
                 1.816167 
                 −1.53733 
               
               
                 22 
                 C 
                 −1.70667 
                 0.61303 
                 0.027252 
               
               
                 23 
                 H 
                 −1.47092 
                 0.437441 
                 1.090885 
               
               
                 24 
                 C 
                 −3.23219 
                 0.705661 
                 −0.10871 
               
               
                 25 
                 H 
                 −3.47774 
                 0.928789 
                 −1.15044 
               
               
                 26 
                 C 
                 −3.87909 
                 −0.61838 
                 0.2801 
               
               
                 27 
                 H 
                 −3.69951 
                 −0.78792 
                 1.353367 
               
               
                 28 
                 C 
                 −3.25514 
                 −1.77173 
                 −0.48128 
               
               
                 29 
                 H 
                 −3.49163 
                 −1.65157 
                 −1.54639 
               
               
                 30 
                 C 
                 −1.7456 
                 −1.72612 
                 −0.30623 
               
               
                 31 
                 H 
                 −1.49212 
                 −1.90797 
                 0.74709 
               
               
                 32 
                 H 
                 −1.27027 
                 −2.4954 
                 −0.91316 
               
               
                 33 
                 O 
                 −1.23626 
                 −0.48478 
                 −0.73658 
               
               
                 34 
                 O 
                 −3.78615 
                 1.76436 
                 0.649212 
               
               
                 35 
                 H 
                 −3.54828 
                 1.64377 
                 1.573515 
               
               
                 36 
                 O 
                 −5.26738 
                 −0.62367 
                 0.01889 
               
               
                 37 
                 H 
                 −5.65398 
                 0.137394 
                 0.460419 
               
               
                 38 
                 O 
                 −3.71483 
                 −3.02085 
                 −0.01174 
               
               
                 39 
                 H 
                 −4.67537 
                 −3.00311 
                 −0.02752 
               
               
                 40 
                 O 
                 0.831964 
                 3.421719 
                 −0.20791 
               
               
                 41 
                 H 
                 1.014034 
                 3.395013 
                 −1.15119 
               
               
                 42 
                 H 
                 0.218065 
                 2.223347 
                 1.27135 
               
            
           
           
               
            
               
                 DB7 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 2.973505 
                 −0.13611 
                 0.449475 
               
               
                 2 
                 C 
                 2.817109 
                 −1.21587 
                 −0.417 
               
               
                 3 
                 C 
                 3.89987 
                 −2.00262 
                 −0.77834 
               
               
                 4 
                 C 
                 5.164133 
                 −1.71962 
                 −0.27799 
               
               
                 5 
                 C 
                 5.333301 
                 −0.64605 
                 0.583984 
               
               
                 6 
                 C 
                 4.245027 
                 0.138274 
                 0.942671 
               
               
                 7 
                 H 
                 1.831657 
                 −1.43672 
                 −0.81156 
               
               
                 8 
                 H 
                 3.757272 
                 −2.84018 
                 −1.45011 
               
               
                 9 
                 H 
                 6.010993 
                 −2.33395 
                 −0.55683 
               
               
                 10 
                 H 
                 6.314935 
                 −0.41851 
                 0.98111 
               
               
                 11 
                 H 
                 4.384538 
                 0.974456 
                 1.61882 
               
               
                 12 
                 C 
                 1.794006 
                 0.728893 
                 0.803031 
               
               
                 13 
                 H 
                 0.924406 
                 0.09224 
                 0.964872 
               
               
                 14 
                 H 
                 1.989022 
                 1.254508 
                 1.740935 
               
               
                 15 
                 C 
                 1.493752 
                 1.757946 
                 −0.29079 
               
               
                 16 
                 H 
                 2.355035 
                 2.42537 
                 −0.37552 
               
               
                 17 
                 H 
                 1.380543 
                 1.250717 
                 −1.25283 
               
               
                 18 
                 C 
                 0.265121 
                 2.629323 
                 −0.01507 
               
               
                 19 
                 C 
                 −1.06286 
                 2.072606 
                 −0.52984 
               
               
                 20 
                 H 
                 −1.83299 
                 2.808147 
                 −0.29365 
               
               
                 21 
                 H 
                 −1.01983 
                 1.984089 
                 −1.62081 
               
               
                 22 
                 C 
                 −1.50782 
                 0.732682 
                 0.02529 
               
               
                 23 
                 H 
                 −1.24118 
                 0.661889 
                 1.093207 
               
               
                 24 
                 C 
                 −3.02536 
                 0.533744 
                 −0.09236 
               
               
                 25 
                 H 
                 −3.31379 
                 0.653297 
                 −1.14011 
               
               
                 26 
                 C 
                 −3.41273 
                 −0.86516 
                 0.372145 
               
               
                 27 
                 H 
                 −3.19827 
                 −0.94217 
                 1.449636 
               
               
                 28 
                 C 
                 −2.59061 
                 −1.92055 
                 −0.34145 
               
               
                 29 
                 H 
                 −2.85296 
                 −1.90104 
                 −1.40705 
               
               
                 30 
                 C 
                 −1.1147 
                 −1.58801 
                 −0.19517 
               
               
                 31 
                 H 
                 −0.82137 
                 −1.66991 
                 0.860875 
               
               
                 32 
                 H 
                 −0.51156 
                 −2.28652 
                 −0.77384 
               
               
                 33 
                 O 
                 −0.84555 
                 −0.29665 
                 −0.69079 
               
               
                 34 
                 O 
                 −3.76197 
                 1.509191 
                 0.61986 
               
               
                 35 
                 H 
                 −3.5131 
                 1.472225 
                 1.548421 
               
               
                 36 
                 O 
                 −4.77703 
                 −1.14175 
                 0.133027 
               
               
                 37 
                 H 
                 −5.29684 
                 −0.44584 
                 0.544253 
               
               
                 38 
                 O 
                 −2.8053 
                 −3.20729 
                 0.196418 
               
               
                 39 
                 H 
                 −3.75228 
                 −3.37009 
                 0.195266 
               
               
                 40 
                 O 
                 0.445632 
                 3.939175 
                 −0.54745 
               
               
                 41 
                 H 
                 0.546362 
                 3.86433 
                 −1.50006 
               
               
                 42 
                 H 
                 0.182669 
                 2.785328 
                 1.064839 
               
            
           
           
               
            
               
                 DB8 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −3.59617 
                 −0.26452 
                 −0.86901 
               
               
                 2 
                 C 
                 −4.55498 
                 −1.11986 
                 −0.32692 
               
               
                 3 
                 C 
                 −5.70699 
                 −0.61913 
                 0.257662 
               
               
                 4 
                 C 
                 −5.92286 
                 0.752225 
                 0.312911 
               
               
                 5 
                 C 
                 −4.98043 
                 1.614372 
                 −0.2252 
               
               
                 6 
                 C 
                 −3.8278 
                 1.107654 
                 −0.81308 
               
               
                 7 
                 H 
                 −4.39199 
                 −2.19115 
                 −0.36275 
               
               
                 8 
                 H 
                 −6.43978 
                 −1.30007 
                 0.67233 
               
               
                 9 
                 H 
                 −6.82203 
                 1.144099 
                 0.770933 
               
               
                 10 
                 H 
                 −5.14005 
                 2.684777 
                 −0.19053 
               
               
                 11 
                 H 
                 −3.09468 
                 1.787923 
                 −1.23154 
               
               
                 12 
                 C 
                 −2.32226 
                 −0.81591 
                 −1.45664 
               
               
                 13 
                 H 
                 −2.56318 
                 −1.65686 
                 −2.11075 
               
               
                 14 
                 H 
                 −1.85313 
                 −0.05248 
                 −2.08192 
               
               
                 15 
                 C 
                 −1.30497 
                 −1.29262 
                 −0.41254 
               
               
                 16 
                 H 
                 −1.72611 
                 −2.10533 
                 0.186695 
               
               
                 17 
                 H 
                 −0.449 
                 −1.70921 
                 −0.9488 
               
               
                 18 
                 C 
                 −0.81305 
                 −0.20926 
                 0.547667 
               
               
                 19 
                 C 
                 0.486619 
                 −0.6109 
                 1.236639 
               
               
                 20 
                 H 
                 0.60943 
                 0.003101 
                 2.13234 
               
               
                 21 
                 H 
                 0.401924 
                 −1.64751 
                 1.571142 
               
               
                 22 
                 C 
                 1.722196 
                 −0.49989 
                 0.352129 
               
               
                 23 
                 H 
                 1.44004 
                 −0.61588 
                 −0.70517 
               
               
                 24 
                 C 
                 2.45636 
                 0.839342 
                 0.496492 
               
               
                 25 
                 H 
                 2.751493 
                 0.96132 
                 1.545173 
               
               
                 26 
                 C 
                 3.707681 
                 0.843004 
                 −0.3651 
               
               
                 27 
                 H 
                 3.400529 
                 0.775416 
                 −1.41877 
               
               
                 28 
                 C 
                 4.573871 
                 −0.35918 
                 −0.04298 
               
               
                 29 
                 H 
                 4.943825 
                 −0.25168 
                 0.984886 
               
               
                 30 
                 C 
                 3.736271 
                 −1.62554 
                 −0.13523 
               
               
                 31 
                 H 
                 3.429726 
                 −1.78215 
                 −1.17853 
               
               
                 32 
                 H 
                 4.319421 
                 −2.48731 
                 0.186443 
               
               
                 33 
                 O 
                 2.608389 
                 −1.54952 
                 0.707214 
               
               
                 34 
                 O 
                 1.667877 
                 1.938536 
                 0.075311 
               
               
                 35 
                 H 
                 1.126424 
                 2.242814 
                 0.805722 
               
               
                 36 
                 O 
                 4.483857 
                 2.006226 
                 −0.16284 
               
               
                 37 
                 H 
                 3.919677 
                 2.765154 
                 −0.33443 
               
               
                 38 
                 O 
                 5.653305 
                 −0.48497 
                 −0.94366 
               
               
                 39 
                 H 
                 6.11843 
                 0.355607 
                 −0.96032 
               
               
                 40 
                 O 
                 −1.74691 
                 0.043957 
                 1.592777 
               
               
                 41 
                 H 
                 −2.58715 
                 0.290815 
                 1.195541 
               
               
                 42 
                 H 
                 −0.64695 
                 0.715959 
                 −0.01897 
               
            
           
           
               
            
               
                 DB9 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 3.673742 
                 −0.21094 
                 0.147739 
               
               
                 2 
                 C 
                 4.604789 
                 −0.45109 
                 −0.85843 
               
               
                 3 
                 C 
                 5.499575 
                 0.534184 
                 −1.25256 
               
               
                 4 
                 C 
                 5.474692 
                 1.780965 
                 −0.6445 
               
               
                 5 
                 C 
                 4.549931 
                 2.033482 
                 0.359813 
               
               
                 6 
                 C 
                 3.659052 
                 1.044894 
                 0.750244 
               
               
                 7 
                 H 
                 4.630904 
                 −1.42358 
                 −1.33747 
               
               
                 8 
                 H 
                 6.219068 
                 0.326271 
                 −2.03498 
               
               
                 9 
                 H 
                 6.172914 
                 2.550448 
                 −0.94893 
               
               
                 10 
                 H 
                 4.524237 
                 3.002731 
                 0.842451 
               
               
                 11 
                 H 
                 2.939289 
                 1.248566 
                 1.535553 
               
               
                 12 
                 C 
                 2.671933 
                 −1.26125 
                 0.545698 
               
               
                 13 
                 H 
                 3.07156 
                 −2.25556 
                 0.329021 
               
               
                 14 
                 H 
                 2.495045 
                 −1.21336 
                 1.621228 
               
               
                 15 
                 C 
                 1.343233 
                 −1.08054 
                 −0.19 
               
               
                 16 
                 H 
                 0.946181 
                 −0.08529 
                 0.020901 
               
               
                 17 
                 H 
                 1.517584 
                 −1.13145 
                 −1.2675 
               
               
                 18 
                 C 
                 0.313973 
                 −2.14601 
                 0.15849 
               
               
                 19 
                 C 
                 −0.99634 
                 −2.01673 
                 −0.62822 
               
               
                 20 
                 H 
                 −0.75946 
                 −1.65945 
                 −1.63312 
               
               
                 21 
                 H 
                 −1.43319 
                 −3.0103 
                 −0.74881 
               
               
                 22 
                 C 
                 −2.12538 
                 −1.13669 
                 −0.0815 
               
               
                 23 
                 H 
                 −2.54297 
                 −1.58718 
                 0.831522 
               
               
                 24 
                 C 
                 −1.75403 
                 0.318738 
                 0.262977 
               
               
                 25 
                 H 
                 −1.17224 
                 0.736734 
                 −0.57081 
               
               
                 26 
                 C 
                 −2.99848 
                 1.178434 
                 0.445033 
               
               
                 27 
                 H 
                 −3.48044 
                 0.863691 
                 1.382105 
               
               
                 28 
                 C 
                 −4.00008 
                 0.980093 
                 −0.67424 
               
               
                 29 
                 H 
                 −3.56777 
                 1.348864 
                 −1.61121 
               
               
                 30 
                 C 
                 −4.29378 
                 −0.50415 
                 −0.8116 
               
               
                 31 
                 H 
                 −4.74727 
                 −0.88112 
                 0.115362 
               
               
                 32 
                 H 
                 −4.98309 
                 −0.69173 
                 −1.63503 
               
               
                 33 
                 O 
                 −3.10171 
                 −1.19109 
                 −1.10943 
               
               
                 34 
                 O 
                 −1.01507 
                 0.406875 
                 1.463825 
               
               
                 35 
                 H 
                 −0.61783 
                 −0.45581 
                 1.665673 
               
               
                 36 
                 O 
                 −2.60074 
                 2.531176 
                 0.539138 
               
               
                 37 
                 H 
                 −3.40644 
                 3.056119 
                 0.550349 
               
               
                 38 
                 O 
                 −5.15334 
                 1.727488 
                 −0.33061 
               
               
                 39 
                 H 
                 −5.67295 
                 1.886755 
                 −1.12064 
               
               
                 40 
                 O 
                 0.099341 
                 −2.10444 
                 1.574182 
               
               
                 41 
                 H 
                 −0.44986 
                 −2.84765 
                 1.834518 
               
               
                 42 
                 H 
                 0.75194 
                 −3.11828 
                 −0.09074 
               
            
           
           
               
            
               
                 DB10 
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 C 
                 −2.01762 
                 −1.56247 
                 −0.02527 
               
               
                 2 
                 C 
                 −1.48471 
                 −2.04159 
                 −1.21624 
               
               
                 3 
                 C 
                 −0.42146 
                 −2.93514 
                 −1.2169 
               
               
                 4 
                 C 
                 0.119498 
                 −3.37461 
                 −0.01902 
               
               
                 5 
                 C 
                 −0.42123 
                 −2.92597 
                 1.179164 
               
               
                 6 
                 C 
                 −1.47996 
                 −2.03285 
                 1.17222 
               
               
                 7 
                 H 
                 −1.89653 
                 −1.7031 
                 −2.16025 
               
               
                 8 
                 H 
                 −0.01339 
                 −3.28318 
                 −2.15765 
               
               
                 9 
                 H 
                 0.953464 
                 −4.06491 
                 −0.01689 
               
               
                 10 
                 H 
                 −0.01264 
                 −3.26916 
                 2.121427 
               
               
                 11 
                 H 
                 −1.88638 
                 −1.68008 
                 2.113625 
               
               
                 12 
                 C 
                 −3.13032 
                 −0.54201 
                 −0.00105 
               
               
                 13 
                 H 
                 −3.51857 
                 −0.39243 
                 −1.01161 
               
               
                 14 
                 H 
                 −3.95587 
                 −0.95163 
                 0.58457 
               
               
                 15 
                 C 
                 −2.73715 
                 0.810597 
                 0.618854 
               
               
                 16 
                 H 
                 −3.61036 
                 1.243955 
                 1.109731 
               
               
                 17 
                 H 
                 −1.99431 
                 0.655272 
                 1.402278 
               
               
                 18 
                 C 
                 −2.25014 
                 1.866658 
                 −0.37277 
               
               
                 19 
                 C 
                 −1.09244 
                 1.497488 
                 −1.30099 
               
               
                 20 
                 H 
                 −1.28008 
                 0.499299 
                 −1.69461 
               
               
                 21 
                 H 
                 −1.12593 
                 2.169849 
                 −2.16168 
               
               
                 22 
                 C 
                 0.359373 
                 1.512077 
                 −0.80323 
               
               
                 23 
                 H 
                 0.743238 
                 2.543326 
                 −0.79657 
               
               
                 24 
                 C 
                 0.618277 
                 0.929348 
                 0.592984 
               
               
                 25 
                 H 
                 0.106509 
                 −0.03627 
                 0.675663 
               
               
                 26 
                 C 
                 2.104264 
                 0.693333 
                 0.822161 
               
               
                 27 
                 H 
                 2.600527 
                 1.672733 
                 0.869546 
               
               
                 28 
                 C 
                 2.723587 
                 −0.08978 
                 −0.31264 
               
               
                 29 
                 H 
                 2.254963 
                 −1.08191 
                 −0.36128 
               
               
                 30 
                 C 
                 2.436378 
                 0.654412 
                 −1.60417 
               
               
                 31 
                 H 
                 2.912995 
                 1.643801 
                 −1.57261 
               
               
                 32 
                 H 
                 2.832418 
                 0.106882 
                 −2.45869 
               
               
                 33 
                 O 
                 1.047336 
                 0.767345 
                 −1.79886 
               
               
                 34 
                 O 
                 0.206608 
                 1.8003 
                 1.630666 
               
               
                 35 
                 H 
                 −0.54395 
                 2.339264 
                 1.331463 
               
               
                 36 
                 O 
                 2.335806 
                 −0.01739 
                 2.024601 
               
               
                 37 
                 H 
                 1.972125 
                 0.500052 
                 2.74756 
               
               
                 38 
                 O 
                 4.122664 
                 −0.20793 
                 −0.16387 
               
               
                 39 
                 H 
                 4.291323 
                 −0.51004 
                 0.732869 
               
               
                 40 
                 O 
                 −1.95456 
                 3.030528 
                 0.410765 
               
               
                 41 
                 H 
                 −1.75088 
                 3.762859 
                 −0.17652 
               
               
                 42 
                 H 
                 −3.09968 
                 2.095686 
                 −1.02549 
               
               
                   
               
            
           
         
       
     
     2. Procedure for Calculating NMRs 
     To calculate NMR shifts for each of the diastereomers, following the procedure by Smith and Goodman (Bokor, et al., 2017, Chem. Rev. 117:1687-1764), the shielding constants in each conformer were averaged using Boltzmann averaging over the conformers i using the equation: 
     
       
         
           
             
               σ 
               x 
             
             = 
             
               
                 
                   ∑ 
                   i 
                 
                  
                 
                   
                     σ 
                     i 
                     x 
                   
                    
                   
                     exp 
                      
                     
                       ( 
                       
                         
                           - 
                           
                             E 
                             i 
                           
                         
                         / 
                         RT 
                       
                       ) 
                     
                   
                 
               
               
                 
                   ∑ 
                   i 
                 
                  
                 
                   exp 
                    
                   
                     ( 
                     
                       
                         - 
                         
                           E 
                           i 
                         
                       
                       / 
                       RT 
                     
                     ) 
                   
                 
               
             
           
         
       
     
     where σ x  is the Boltzmann averaged shielding constant for nucleus x, σ i   x  is the shielding constant for nucleus x in conformer i, and E is the potential energy of conformer i (relative to the global minimum), obtained from the calculation. The temperature T was taken as 298 K. 
     Averaged shielding constants for each nuclei of the two diastereomers were then scaled using following equation: 
     
       
         
           
             
               δ 
               scaled 
             
             = 
             
               
                 
                   σ 
                   calc 
                 
                 - 
                 intercept 
               
               slope 
             
           
         
       
     
     where the slope and intercept (Table 5) were obtained from a plot of the calculated vs experimental data for a test set of molecules used by Pierens (Mandal, et al., 2016, Synth. Commun. 46:1327-1342). 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Intercept and slope values calculated for the test set 
               
               
                 of molecules 14  using ωB97XD/def2TZVP method in methanol. 
               
            
           
           
               
               
               
               
            
               
                   
                 intercept 
                 slope 
                 R 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                   1 H 
                 32.041 
                 −1.081 
                 0.9947 
               
               
                   
                   13 C 
                 188.78 
                 −1.048 
                 0.9987 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 NMR shielding constants calculated using GIAO method with ωB97XD/def2TZVP 
               
               
                 in methanol for the conformers of DA with scaled values 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 DA1 
                 DA2 
                 DA3 
                 DA4 
                 DA5 
                 DA6 
                 DA7 
                 DA8 
                 DA9 
                 DA10 
                 
                   DA 
                 
                 Scale d 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 C 
                 35.418 
                 35.213 
                 35.710 
                 35.068 
                 35.296 
                 35.880 
                 34.978 
                 34.336 
                 34.980 
                 35.019 
                 35.210 
                 146.550 
               
               
                 2 
                 C 
                 53.531 
                 53.380 
                 53.265 
                 53.419 
                 53.510 
                 53.200 
                 53.242 
                 52.479 
                 53.239 
                 53.696 
                 53.323 
                 129.265 
               
               
                 3 
                 C 
                 53.269 
                 53.310 
                 53.227 
                 53.274 
                 53.276 
                 53.174 
                 53.344 
                 54.067 
                 53.344 
                 53.364 
                 53.352 
                 129.237 
               
               
                 4 
                 C 
                 56.806 
                 56.866 
                 56.696 
                 56.912 
                 56.773 
                 56.658 
                 56.920 
                 57.624 
                 56.920 
                 56.874 
                 56.893 
                 125.858 
               
               
                 5 
                 C 
                 53.234 
                 53.253 
                 53.152 
                 53.291 
                 53.169 
                 53.312 
                 53.190 
                 54.041 
                 53.190 
                 53.452 
                 53.314 
                 129.274 
               
               
                 6 
                 C 
                 53.132 
                 53.224 
                 53.372 
                 53.205 
                 53.067 
                 53.392 
                 53.299 
                 54.199 
                 53.301 
                 53.083 
                 53.302 
                 129.285 
               
               
                 7 
                 H 
                 24.218 
                 24.207 
                 24.210 
                 24.212 
                 24.206 
                 24.164 
                 24.209 
                 24.219 
                 24.209 
                 24.215 
                 24.208 
                 7.249 
               
               
                 8 
                 H 
                 24.118 
                 24.117 
                 24.117 
                 24.112 
                 24.111 
                 24.100 
                 24.126 
                 24.224 
                 24.126 
                 24.131 
                 24.126 
                 7.324 
               
               
                 9 
                 H 
                 24.254 
                 24.256 
                 24.245 
                 24.254 
                 24.240 
                 24.242 
                 24.259 
                 24.331 
                 24.259 
                 24.258 
                 24.259 
                 7.202 
               
               
                 10 
                 H 
                 24.117 
                 24.118 
                 24.104 
                 24.118 
                 24.095 
                 24.118 
                 24.111 
                 24.143 
                 24.111 
                 24.107 
                 24.115 
                 7.335 
               
               
                 11 
                 H 
                 24.181 
                 24.183 
                 24.200 
                 24.184 
                 24.153 
                 24.206 
                 24.203 
                 24.140 
                 24.203 
                 24.122 
                 24.178 
                 7.276 
               
               
                 12 
                 C 
                 151.360 
                 151.625 
                 157.817 
                 150.687 
                 151.524 
                 151.978 
                 156.559 
                 149.623 
                 156.559 
                 152.913 
                 152.801 
                 34.334 
               
               
                 13 
                 H 
                 28.812 
                 28.857 
                 29.309 
                 28.772 
                 28.772 
                 29.368 
                 29.281 
                 29.281 
                 29.280 
                 29.525 
                 29.077 
                 2.743 
               
               
                 14 
                 H 
                 29.341 
                 29.391 
                 29.328 
                 29.410 
                 29.367 
                 29.302 
                 29.011 
                 28.797 
                 29.011 
                 28.949 
                 29.220 
                 2.611 
               
               
                 15 
                 C 
                 140.036 
                 141.652 
                 142.654 
                 143.498 
                 143.913 
                 142.647 
                 143.517 
                 146.063 
                 143.522 
                 146.041 
                 142.937 
                 43.748 
               
               
                 16 
                 H 
                 30.241 
                 30.407 
                 30.095 
                 30.335 
                 30.017 
                 30.483 
                 30.163 
                 30.133 
                 30.163 
                 30.204 
                 30.241 
                 1.666 
               
               
                 17 
                 H 
                 30.645 
                 30.418 
                 30.298 
                 30.251 
                 30.775 
                 30.212 
                 30.313 
                 29.999 
                 30.313 
                 30.229 
                 30.376 
                 1.541 
               
               
                 18 
                 C 
                 114.962 
                 111.499 
                 116.847 
                 115.453 
                 115.309 
                 110.637 
                 112.987 
                 108.473 
                 112.988 
                 114.429 
                 113.334 
                 71.998 
               
               
                 19 
                 H 
                 27.837 
                 27.956 
                 27.677 
                 28.240 
                 28.139 
                 27.984 
                 27.802 
                 27.907 
                 27.802 
                 27.866 
                 27.917 
                 3.816 
               
               
                 20 
                 C 
                 139.021 
                 146.634 
                 141.975 
                 141.124 
                 144.145 
                 149.039 
                 149.373 
                 146.294 
                 149.371 
                 149.873 
                 145.215 
                 41.574 
               
               
                 21 
                 H 
                 30.062 
                 29.972 
                 29.943 
                 30.044 
                 30.242 
                 29.466 
                 29.852 
                 29.986 
                 29.851 
                 29.804 
                 29.938 
                 1.946 
               
               
                 22 
                 H 
                 30.479 
                 30.556 
                 30.175 
                 29.918 
                 30.068 
                 30.654 
                 30.234 
                 30.588 
                 30.234 
                 30.002 
                 30.329 
                 1.585 
               
               
                 23 
                 C 
                 109.999 
                 102.739 
                 109.250 
                 109.816 
                 108.624 
                 102.576 
                 102.628 
                 102.749 
                 102.633 
                 110.445 
                 106.177 
                 78.827 
               
               
                 24 
                 H 
                 28.259 
                 28.394 
                 28.356 
                 28.525 
                 28.776 
                 28.398 
                 28.427 
                 28.467 
                 28.427 
                 28.249 
                 28.411 
                 3.359 
               
               
                 25 
                 C 
                 107.099 
                 110.986 
                 107.017 
                 109.583 
                 110.141 
                 110.869 
                 110.822 
                 111.002 
                 110.822 
                 111.855 
                 109.859 
                 75.313 
               
               
                 26 
                 H 
                 28.532 
                 28.653 
                 28.509 
                 28.573 
                 28.702 
                 28.570 
                 28.567 
                 28.707 
                 28.567 
                 28.597 
                 28.597 
                 3.187 
               
               
                 27 
                 C 
                 106.158 
                 106.512 
                 106.201 
                 106.661 
                 106.215 
                 106.495 
                 106.490 
                 106.578 
                 106.487 
                 105.784 
                 106.355 
                 78.658 
               
               
                 28 
                 H 
                 28.426 
                 28.474 
                 28.430 
                 28.478 
                 28.565 
                 28.448 
                 28.458 
                 28.522 
                 28.458 
                 28.425 
                 28.465 
                 3.309 
               
               
                 29 
                 C 
                 112.925 
                 113.609 
                 112.911 
                 113.319 
                 113.175 
                 113.605 
                 113.570 
                 113.712 
                 113.568 
                 112.977 
                 113.326 
                 72.005 
               
               
                 30 
                 H 
                 28.328 
                 28.291 
                 28.297 
                 28.325 
                 28.324 
                 28.276 
                 28.273 
                 28.380 
                 28.273 
                 28.215 
                 28.300 
                 3.462 
               
               
                 31 
                 C 
                 114.715 
                 115.319 
                 114.671 
                 115.141 
                 114.912 
                 115.341 
                 115.300 
                 115.446 
                 115.300 
                 115.403 
                 115.132 
                 70.281 
               
               
                 32 
                 H 
                 28.661 
                 28.606 
                 28.643 
                 28.801 
                 28.766 
                 28.603 
                 28.613 
                 28.715 
                 28.613 
                 28.578 
                 28.656 
                 3.133 
               
               
                 33 
                 H 
                 28.097 
                 27.983 
                 28.060 
                 28.131 
                 28.038 
                 27.990 
                 27.980 
                 28.140 
                 27.980 
                 27.805 
                 28.024 
                 3.718 
               
               
                 34 
                 O 
                 276.811 
                 278.871 
                 276.281 
                 277.675 
                 283.299 
                 278.289 
                 279.229 
                 279.458 
                 279.237 
                 276.586 
                 278.453 
               
               
                 35 
                 O 
                 301.618 
                 301.084 
                 301.983 
                 291.476 
                 301.318 
                 300.815 
                 301.059 
                 301.024 
                 301.050 
                 300.357 
                 300.372 
               
               
                 36 
                 H 
                 29.729 
                 29.858 
                 29.777 
                 29.046 
                 29.909 
                 29.776 
                 29.799 
                 29.865 
                 29.799 
                 29.808 
                 29.746 
                 2.124 
               
               
                 37 
                 O 
                 300.850 
                 300.417 
                 300.873 
                 300.742 
                 300.338 
                 300.365 
                 300.366 
                 300.389 
                 300.358 
                 299.661 
                 300.468 
               
               
                 38 
                 H 
                 29.601 
                 29.571 
                 29.604 
                 29.576 
                 29.616 
                 29.541 
                 29.544 
                 29.595 
                 29.545 
                 29.538 
                 29.575 
                 2.282 
               
               
                 39 
                 O 
                 304.728 
                 305.014 
                 304.747 
                 304.758 
                 304.725 
                 305.172 
                 305.120 
                 305.157 
                 305.102 
                 304.579 
                 304.904 
               
               
                 40 
                 H 
                 30.635 
                 30.571 
                 30.618 
                 30.644 
                 30.627 
                 30.557 
                 30.558 
                 30.632 
                 30.559 
                 30.529 
                 30.595 
                 1.339 
               
               
                 41 
                 O 
                 282.471 
                 279.035 
                 286.101 
                 279.502 
                 276.535 
                 274.885 
                 281.411 
                 273.449 
                 281.411 
                 276.442 
                 279.392 
               
               
                 42 
                 H 
                 32.235 
                 28.324 
                 31.349 
                 27.673 
                 31.870 
                 28.450 
                 28.669 
                 28.895 
                 28.668 
                 31.472 
                 29.844 
                 2.033 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE.7 
               
             
            
               
                   
               
               
                 NMR shielding constants calculated using GIAO method with ωB97XD/def2TZVP 
               
               
                 in methanol for the conformers of DB with scaled values 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 DB1 
                 DB2 
                 DB3 
                 DB4 
                 DB5 
                 DB6 
                 DB7 
                 DB8 
                 DB9 
                 DB10 
                 
                   DB 
                 
                 Scale d 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 C 
                 35.378 
                 37.066 
                 37.182 
                 36.493 
                 37.026 
                 35.188 
                 35.626 
                 37.046 
                 35.872 
                 35.128 
                 36.201 
                 145.604 
               
               
                 2 
                 C 
                 53.148 
                 51.512 
                 51.328 
                 53.741 
                 51.678 
                 53.093 
                 53.216 
                 52.440 
                 53.377 
                 50.930 
                 52.445 
                 130.103 
               
               
                 3 
                 C 
                 53.226 
                 53.971 
                 54.066 
                 53.142 
                 53.949 
                 53.193 
                 53.405 
                 52.142 
                 53.203 
                 53.312 
                 53.361 
                 129.229 
               
               
                 4 
                 C 
                 56.839 
                 56.663 
                 56.721 
                 56.463 
                 56.662 
                 56.841 
                 56.722 
                 55.411 
                 56.681 
                 55.964 
                 56.497 
                 126.237 
               
               
                 5 
                 C 
                 53.300 
                 53.152 
                 53.235 
                 53.087 
                 53.096 
                 53.296 
                 53.284 
                 52.267 
                 53.243 
                 52.120 
                 53.008 
                 129.566 
               
               
                 6 
                 C 
                 53.497 
                 53.307 
                 53.356 
                 53.065 
                 53.360 
                 53.605 
                 53.711 
                 53.672 
                 53.184 
                 51.642 
                 53.240 
                 129.345 
               
               
                 7 
                 H 
                 24.183 
                 24.059 
                 24.082 
                 23.967 
                 24.137 
                 24.157 
                 24.091 
                 24.040 
                 24.195 
                 24.223 
                 24.113 
                 7.336 
               
               
                 8 
                 H 
                 24.118 
                 24.116 
                 24.150 
                 24.121 
                 24.138 
                 24.100 
                 24.102 
                 24.015 
                 24.116 
                 24.144 
                 24.112 
                 7.338 
               
               
                 9 
                 H 
                 24.256 
                 24.231 
                 24.246 
                 24.232 
                 24.241 
                 24.248 
                 24.252 
                 24.165 
                 24.240 
                 24.208 
                 24.232 
                 7.227 
               
               
                 10 
                 H 
                 24.117 
                 24.087 
                 24.093 
                 24.082 
                 24.089 
                 24.118 
                 24.127 
                 24.072 
                 24.092 
                 24.019 
                 24.090 
                 7.358 
               
               
                 11 
                 H 
                 24.218 
                 24.191 
                 24.197 
                 24.147 
                 24.190 
                 24.220 
                 24.196 
                 24.129 
                 24.161 
                 24.010 
                 24.166 
                 7.288 
               
               
                 12 
                 C 
                 151.244 
                 154.774 
                 154.385 
                 151.544 
                 154.244 
                 151.070 
                 151.570 
                 149.957 
                 151.447 
                 155.040 
                 152.530 
                 34.593 
               
               
                 13 
                 H 
                 29.366 
                 28.967 
                 28.926 
                 28.913 
                 28.878 
                 29.368 
                 29.156 
                 28.782 
                 29.420 
                 29.555 
                 29.133 
                 2.691 
               
               
                 14 
                 H 
                 28.862 
                 29.138 
                 29.169 
                 29.123 
                 29.104 
                 28.823 
                 29.352 
                 29.289 
                 28.797 
                 28.744 
                 29.040 
                 2.777 
               
               
                 15 
                 C 
                 138.919 
                 145.718 
                 143.272 
                 144.909 
                 147.124 
                 141.593 
                 139.987 
                 147.007 
                 143.772 
                 150.505 
                 144.286 
                 42.461 
               
               
                 16 
                 H 
                 30.475 
                 30.164 
                 30.214 
                 29.958 
                 30.163 
                 30.734 
                 30.114 
                 30.371 
                 29.580 
                 29.580 
                 30.135 
                 1.763 
               
               
                 17 
                 H 
                 30.327 
                 30.552 
                 30.419 
                 30.221 
                 30.451 
                 29.889 
                 30.118 
                 29.731 
                 30.424 
                 29.818 
                 30.195 
                 1.708 
               
               
                 18 
                 C 
                 116.779 
                 121.735 
                 121.637 
                 116.042 
                 122.481 
                 110.833 
                 112.337 
                 113.397 
                 114.781 
                 112.965 
                 116.302 
                 69.165 
               
               
                 19 
                 C 
                 138.613 
                 150.169 
                 139.272 
                 147.005 
                 145.128 
                 145.416 
                 144.005 
                 142.856 
                 144.150 
                 149.632 
                 144.633 
                 42.129 
               
               
                 20 
                 H 
                 30.632 
                 30.159 
                 30.662 
                 29.954 
                 30.056 
                 29.418 
                 29.323 
                 30.263 
                 30.460 
                 30.013 
                 30.093 
                 1.802 
               
               
                 21 
                 H 
                 29.940 
                 30.421 
                 30.087 
                 29.850 
                 30.851 
                 30.735 
                 30.589 
                 30.391 
                 29.429 
                 29.742 
                 30.204 
                 1.700 
               
               
                 22 
                 C 
                 107.873 
                 104.470 
                 108.024 
                 107.530 
                 108.929 
                 106.129 
                 107.086 
                 108.304 
                 108.536 
                 109.096 
                 107.595 
                 77.474 
               
               
                 23 
                 H 
                 28.550 
                 28.555 
                 28.869 
                 28.412 
                 28.735 
                 28.993 
                 28.745 
                 28.991 
                 28.414 
                 28.757 
                 28.702 
                 3.090 
               
               
                 24 
                 C 
                 110.682 
                 113.472 
                 110.884 
                 114.787 
                 108.429 
                 109.517 
                 109.309 
                 105.870 
                 111.256 
                 113.993 
                 110.820 
                 74.397 
               
               
                 25 
                 H 
                 28.253 
                 28.626 
                 28.329 
                 27.774 
                 29.090 
                 29.056 
                 28.949 
                 28.654 
                 28.581 
                 30.173 
                 28.749 
                 3.046 
               
               
                 26 
                 C 
                 104.871 
                 106.394 
                 104.967 
                 105.426 
                 103.714 
                 103.615 
                 103.618 
                 106.144 
                 104.940 
                 103.431 
                 104.712 
                 80.225 
               
               
                 27 
                 H 
                 28.450 
                 28.588 
                 28.596 
                 28.427 
                 28.678 
                 28.663 
                 28.598 
                 28.484 
                 28.449 
                 28.884 
                 28.582 
                 3.201 
               
               
                 28 
                 C 
                 113.595 
                 114.365 
                 113.632 
                 113.052 
                 114.066 
                 114.146 
                 114.153 
                 113.971 
                 113.336 
                 115.879 
                 114.021 
                 71.342 
               
               
                 29 
                 H 
                 28.353 
                 28.259 
                 28.406 
                 27.858 
                 28.362 
                 28.315 
                 28.103 
                 28.247 
                 28.427 
                 29.156 
                 28.349 
                 3.417 
               
               
                 30 
                 C 
                 116.126 
                 116.255 
                 116.190 
                 114.735 
                 116.707 
                 117.078 
                 116.786 
                 116.052 
                 116.120 
                 117.398 
                 116.345 
                 69.124 
               
               
                 31 
                 H 
                 28.749 
                 28.717 
                 28.862 
                 28.627 
                 28.744 
                 28.770 
                 28.569 
                 28.627 
                 28.745 
                 28.997 
                 28.741 
                 3.054 
               
               
                 32 
                 H 
                 28.165 
                 27.914 
                 28.221 
                 27.938 
                 28.109 
                 28.181 
                 27.676 
                 27.972 
                 28.167 
                 28.303 
                 28.064 
                 3.680 
               
               
                 33 
                 O 
                 277.171 
                 280.739 
                 277.358 
                 280.987 
                 283.220 
                 276.278 
                 278.248 
                 276.673 
                 276.848 
                 279.114 
                 278.667 
               
               
                 34 
                 O 
                 294.824 
                 304.884 
                 294.746 
                 300.218 
                 299.916 
                 297.959 
                 297.636 
                 305.825 
                 285.610 
                 292.277 
                 297.399 
               
               
                 35 
                 H 
                 29.877 
                 30.981 
                 30.015 
                 29.816 
                 31.930 
                 31.823 
                 31.781 
                 30.291 
                 26.828 
                 27.175 
                 30.054 
                 1.839 
               
               
                 36 
                 O 
                 299.772 
                 300.740 
                 299.797 
                 299.262 
                 300.016 
                 299.231 
                 299.204 
                 301.272 
                 296.751 
                 302.594 
                 299.866 
               
               
                 37 
                 H 
                 29.592 
                 29.696 
                 29.653 
                 29.393 
                 29.609 
                 29.591 
                 29.544 
                 29.513 
                 29.600 
                 30.062 
                 29.625 
                 2.236 
               
               
                 38 
                 O 
                 304.195 
                 303.840 
                 304.278 
                 303.703 
                 303.586 
                 303.334 
                 303.135 
                 303.304 
                 304.996 
                 306.911 
                 304.128 
               
               
                 39 
                 H 
                 30.626 
                 29.994 
                 30.674 
                 30.479 
                 30.069 
                 30.054 
                 29.958 
                 29.998 
                 30.603 
                 30.209 
                 30.266 
                 1.643 
               
               
                 40 
                 O 
                 269.833 
                 282.227 
                 271.289 
                 270.523 
                 298.437 
                 272.454 
                 257.246 
                 269.539 
                 278.286 
                 270.583 
                 274.059 
               
               
                 41 
                 H 
                 32.160 
                 28.700 
                 32.205 
                 31.558 
                 30.741 
                 31.797 
                 31.325 
                 32.164 
                 30.295 
                 30.491 
                 31.141 
                 0.833 
               
               
                 42 
                 H 
                 27.882 
                 28.324 
                 28.323 
                 27.945 
                 28.435 
                 28.398 
                 28.450 
                 27.975 
                 27.673 
                 27.736 
                 28.114 
                 3.634 
               
               
                   
               
            
           
         
       
     
     3. Calculation of the CP3 and the Probability Parameters 
     Using the applet available at www-jmgdotchdotcamdotacdotuk/tools/nmr/, the values of the CP3 parameter and corresponding probability for the assignment of the pair of diastereoisomers developed by Smith and Goodman were calculated (Bokor, et al., 2017, Chem. Rev. 117:1687-1764). The CP3 parameter is based on comparing differences in experimental and calculated NMR shifts and combined with Bayes&#39; theorem to obtain quantifiable confidence of diastereomer assignment. Values for the CP3 parameter obtained from the applet are shown in Table 8. 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 CP3 parameter and the probability factor obtained 
               
               
                 from the Smith and Goodman calculations. 
               
            
           
           
               
               
               
               
            
               
                   
                 C data 
                 H data 
                 All data 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 CP3 
                   
                   
                   
               
               
                   
                 3a-DA &amp; 3a′-DB 
                 0.36 
                 0.29 
                 0.33 
               
               
                   
                 3a-DB &amp; 3a′-DA 
                 −0.57 
                 −0.45 
                 −0.51 
               
               
                   
                 probability 
               
               
                   
                 3a-DA &amp; 3a′-DB 
                 100.0% 
                 98.3% 
                 100.0% 
               
               
                   
                 3a-DB &amp; 3a′-DA 
                 0.0% 
                 1.7% 
                 0.0% 
               
               
                   
                   
               
            
           
         
       
     
     The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. The appended claims are intended to be construed to include all such embodiments and equivalent variations.