PATENT ABSTRACT
This invention relates generally to enantiomerically enriched C—H activated ruthenium olefin metathesis catalyst compounds which are stereogenic at ruthenium, to the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in enantio- and Z-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

PATENT DESCRIPTION
RELATED APPLICATIONS 
       [0001]    This application claims the benefit of U.S. Provisional Patent Application No. 61/823,539, filed May 15, 2013, U.S. Provisional Patent Application No. 61/838,673, filed Jun. 24, 2013, and U.S. Provisional Patent Application No. 61/933,586, filed Jan. 30, 2014, the contents of each are incorporated herein by reference. 
     
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT 
       [0002]    This invention was made with government support under Grant No. 5R01GM031332-27 awarded by the National Institutes of Health and Grant No. CHE-1048404 awarded by the National Science Foundation. The U.S. Government has certain rights in this invention. 
     
    
     TECHNICAL FIELD 
       [0003]    This invention relates generally to enantiomerically enriched C—H activated ruthenium olefin metathesis catalyst compounds which are stereogenic at ruthenium, to the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in enantio- and Z-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry. 
       BACKGROUND 
       [0004]    Since its discovery in the 1950s, olefin metathesis has emerged as a valuable synthetic method for the formation of carbon-carbon double bonds. In particular, its recent advances in applications to organic syntheses and polymer syntheses mostly rely on developments of well-defined catalysts (see (a) Cossy, J.; Arseniyadis, S.; Meyer, C.,  Metathesis in Natural Product Synthesis: Strategies, Substrates, and Catalysts.  1st ed.; Wiley-VCH: Weinheim, Germany, 2010; (b) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D.,  Angew. Chem., Int. Ed.  2005, 44, 4490-4527; (c) Mutlu, H.; de Espinosa, L. M.; Meier, M. A. R.,  Chem. Soc. Rev.  2011, 40, 1404-1445; (d) Leitgeb, A.; Wappel, J.; Slugovc, C.,  Polymer  2010, 51, 2927-2946; (e) Buchmeiser, M. R.,  Macromol. Symp.  2010, 298, 17-24; (f) Sutthasupa, S.; Shiotsuki, M.; Sanda, F.,  Polymer J.  2010, 42, 905-915; (g) Binder, J. B.; Raines, R. T.,  Curr. Opin. Chem. Biol.  2008, 12, 767-773). Among attempts to improve catalyst efficiency over the past decade, one of the most attractive frontiers has been selective synthesis of stereo-controlled olefin product. However, most catalysts give higher proportion of thermodynamically favored E isomer of olefin in products. This fundamental nature of olefin metathesis limits its applications to some reactions including natural product synthesis. Furthermore, asymmetric olefin metathesis methodologies are desirable for the synthesis of enantiopure natural products and other biologically-relevant molecules (see Hoveyda, A. H.; Malcolmson, S. J.; Meek, S. J.; Zhugralin, A. R.,  Angew. Chem., Int. Ed.  2010, 49, 34-44). Thus, an enantioselective catalyst which also gives high Z-isomer of olefin product is expected to open a new convenient route to value-added products. Consequently, the development of chiral catalysts for methods such as asymmetric ring opening/cross metathesis (AROCM) is a field of ongoing interest (see Kress, S.; Blechert, S.,  Chem. Soc. Rev.  2012, 41, 4389-4408). 
         [0005]    The earliest examples of such catalysts contained Molybdenum, and while capable of generating AROCM products in high ee (80-90%), suffered from limited substrate scope and functional group compatibility (see (a) Fujimura, O.; Grubbs, R. H.,  J. Am. Chem. Soc.  1996, 118, 2499-2500; (b) Fujimura, O.; Grubbs, R. H.,  J. Org. Chem.  1998, 63, 824-832; (c) La, D. S.; Ford, J. G.; Sattely, E. S.; Bonitatebus, P. J.; Schrock, R. R.; Hoveyda, A. H.,  J. Am. Chem. Soc.  1999, 121, 11603-11604; (d) La, D. S.; Sattely, E. S.; Ford, J. G.; Schrock, R. R.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2001, 123, 7767-7778; (e) Tsang, W. C. P.; Jernelius, J. A.; Cortez, G. A.; Weatherhead, G. S.; Schrock, R. R.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2003, 125, 2591-2596). Ruthenium-based catalysts have been developed wherein the chirality is built into the N-heterocyclic carbene (NHC) ligand (see (a) Seiders, T. J.; Ward, D. W.; Grubbs, R. H.,  Org. Lett.  2001, 3, 3225-3228; (b) Berlin, J. M.; Goldberg, S. D.; Grubbs, R. H.,  Angew. Chem., Int. Ed.  2006, 45, 7591-7595; (c) Funk, T. W.; Berlin, J. M.; Grubbs, R. H.,  J. Am. Chem. Soc.  2006, 128, 1840-1846; (d) Savoie, J.; Stenne, B.; Collins, S. K.,  Adv. Synth. Catal.  2009, 351, 1826-1832; (e) Stenne, B.; Timperio, J.; Savoie, J.; Dudding, T.; Collins, S. K.,  Org. Lett.  2010, 12, 2032-2035; (f) Tiede, S.; Berger, A.; Schlesiger, D.; Rost, D.; Luehl, A.; Blechert, S.,  Angew. Chem., Int. Ed.  2010, 49, 3972-3975; (g) Kannenberg, A.; Rost, D.; Eibauer, S.; Tiede, S.; Blechert, S.,  Angew. Chem., Int. Ed.  2011, 50, 3299-3302; (h) Van Veldhuizen, J. J.; Garber, S. B.; Kingsbury, J. S.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2002, 124, 4954-4955; (i) Van Veldhuizen, J. J.; Gillingham, D. G.; Garber, S. B.; Kataoka, O.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2003, 125, 12502-12508; (j) Van Veldhuizen, J. J.; Campbell, J. E.; Giudici, R. E.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2005, 127, 6877-6882). Most of these molybdenum and ruthenium catalyst are capable of performing AROCM with high levels of E-selectivity (up to &gt;98% E) (For an early example of Z-selective ROCM see (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L.,  J. Am. Chem. Soc.  1995, 117, 9610-9611; (b) Tallarico, J. A.; Randall, M. L.; Snapper, M. L.,  Tetrahedron  1997, 53, 16511-16520). More recently, Z-selective AROCM of oxabicycles has been achieved with molybdenum catalysts (see (a) Ibrahem, I.; Yu, M.; Schrock, R. R.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2009, 131, 3844-3845; (b) Yu, M.; Ibrahem, I.; Hasegawa, M.; Schrock, R. R.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2012, 134, 2788-2799). While Z-selective AROCM has been accomplished with ruthenium catalysts, thus far it has been limited to reactions involving heteroatom-substituted α-olefin cross partners (see (a) Khan, R. K. M.; O&#39;Brien, R. V.; Torker, S.; Li, B.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2012, 134, 12774-12779; (b) Khan, R. K. M.; Zhugralin, A. R.; Torker, S.; O&#39;Brien, R. V.; Lombardi, P. J.; Hoveyda, A. H.,  J. Am. Chem. Soc.  2012, 134, 12438-12441). 
         [0006]    The formation of multiple stereocenters in a single catalytic transformation is a powerful approach to the synthesis of stereochemically complex targets. While the development of such a transformation must overcome the challenge of simultaneously controlling diastereo- and enantioselectivity, the end result can reduce the step count of a synthesis and improve its atom economy. One commonly encountered motif is the vicinal diol, which is pervasive throughout natural products and ligands for asymmetric transformations. While the problem of introducing vicinal diols in high enantiopurity has largely been solved by the Sharpless asymmetric dihydroxylation (AD), the formation of 1,2-anti diols remains challenging due to the low enantioselectivity observed in the AD of cis-1,2 disubstituted alkenes (see H. C. Kolb, M. S. Vannieuwenhze, K. B. Sharpless,  Chem. Rev.  1994, 94, 2483-2547). Accordingly, a number of methods have been developed for the enantioselective formation of 1,2-anti diols, including asymmetric epoxidation/hydrolysis (see (a) S. M. Lim, N. Hill, A. G. Myers,  J. Am. Chem. Soc.  2009, 131, 5763-5765; (b) L. Albrecht, H. Jiang, G. Dickmeiss, B. Gschwend, S. G. Hansen, K. A. Jorgensen,  J. Am. Chem. Soc.  2010, 132, 9188-9196), glycolate aldol (see (a) T. Mukaiyama, N. Iwasawa,  Chem. Lett.  1984, 753-756; (b) D. A. Evans, J. R. Gage, J. L. Leighton, A. S. Kim,  J. Org. Chem.  1992, 57, 1961-1963; (c) W. Notz, B. List,  J. Am. Chem. Soc.  2000, 122, 7386-7387; (d) M. T. Crimmins, P. J. McDougall,  Org. Lett.  2003, 5, 591-594; (e) A. B. Northrup, D. W. C. MacMillan,  Science  2004, 305, 1752-1755; (f) A. B. Northrup, I. K. Mangion, F. Hettche, D. W. C. MacMillan,  Angew. Chem.  2004, 116, 2204-2206 ; Angew. Chem., Int. Ed.  2004, 43, 2152-2154; (g) S. E. Denmark, W.-J. Chung,  Angew. Chem.  2008, 120, 1916-1918;  Angew. Chem., Int. Ed.  2008, 47, 1890-1892), iterative cross metathesis/allylic substitution (see (a) J. K. Park, D. T. McQuade,  Angew. Chem.  2012, 124, 2771-2775 ; Angew. Chem., Int. Ed.  2012, 51, 2717-2721; (b) D. Kim, J. S. Lee, S. B. Kong, H. Han,  Angew. Chem.  2013, 125, 4297-4300 ; Angew. Chem., Int. Ed.  2013, 52, 4203-4206), nucleophilic addition to aldehydes (see (a) E. El-Sayed, N. K. Anand, E. M. Carreira,  Org. Lett.  2001, 3, 3017-3020; (b) T. Luanphaisarnnont, C. O. Ndubaku, T. F. Jamison,  Org. Lett.  2005, 7, 2937-2940; (c) S. B. Han, H. Han, M. J. Krische,  J. Am. Chem. Soc.  2010, 132, 1760-1761), desymmetrizing monofunctionalization (see Y. Zhao, J. Rodrigo, A. H. Hoveyda, M. L. Snapper,  Nature  2006, 443, 67-70), and allene hydroboration/aldehyde allylation (see H. C. Brown, G. Narla,  J. Org. Chem.  1995, 60, 4686-4687). In contrast to many of these methods, an asymmetric ring opening/cross metathesis (AROCM) approach (Scheme 4) would consolidate the transformation into a single step and generate a differentiated 1,5-diene fragment in a convergent manner. 
         [0007]    Asymmetric olefin metathesis is a powerful C—C bond forming reaction and has enabled the synthesis of stereochemically complex bioactive compounds (see A. H. Hoveyda, S. J. Malcolmson, S. J. Meek, A. R. Zhugralin,  Angew. Chem.  2010, 122, 38-49 ; Angew. Chem., Int. Ed.  2010, 49, 34-44). Advances in stereoselective olefin metathesis have resulted in the development of catalysts capable of forming products with high diastereo- and enantioselectivity (For a recent review, see A. Fürstner,  Science  2013, 341, 1229713. For leading references, see (a) K. Endo, R. H. Grubbs,  J. Am. Chem. Soc.  2011, 133, 8525-8527; (b) B. K. Keitz, K. Endo, P. R. Patel, M. B. Herbert, R. H. Grubbs,  J. Am. Chem. Soc.  2012, 134, 693-699; (c) L. E. Rosebrugh, M. B. Herbert, V. M. Marx, B. K. Keitz, R. H. Grubbs,  J. Am. Chem. Soc.  2013, 135, 1276-1279; (d) M. M. Flook, A. J. Jiang, R. R. Schrock, P. Mueller, A. H. Hoveyda,  J. Am. Chem. Soc.  2009, 131, 7962-7963; (e) S. J. Meek, R. V. O&#39;Brien, J. Llaveria, R. R. Schrock, A. H. Hoveyda,  Nature  2011, 471, 461-466; (f) R. K. M. Khan, S. Torker, A. H. Hoveyda,  J. Am. Chem. Soc.  2013, 135, 10258; For a recent review, see (a) S. Kress, S. Blechert,  Chem. Soc. Rev.  2012, 41, 4389-4408; for leading references, see (b) J. M. Berlin, S. D. Goldberg, R. H. Grubbs,  Angew. Chem.  2006, 118, 7753-7757 ; Angew. Chem., Int. Ed.  2006, 45, 7591-7595; (c) T. W. Funk, J. M. Berlin, R. H. Grubbs,  J. Am. Chem. Soc.  2006, 128, 1840-1846; (d) J. Savoie, B. Stenne, S. K. Collins,  Adv. Synth. Catal.  2009, 351, 1826-1832; (e) B. Stenne, J. Timperio, J. Savoie, T. Dudding, S. K. Collins,  Org. Lett.  2010, 12, 2032-2035; (f) S. Tiede, A. Berger, D. Schlesiger, D. Rost, A. Luhl, S. Blechert,  Angew. Chem.  2010, 122, 4064-4067 ; Angew. Chem., Int. Ed.  2010, 49, 3972-3975; (g) A. Kannenberg, D. Rost, S. Eibauer, S. Tiede, S. Blechert,  Angew. Chem.  2011, 123, 3357-3360 ; Angew. Chem., Int. Ed.  2011, 50, 3299-3302; (h) R. K. M. Khan, R. V. O&#39;Brien, S. Torker, B. Li, A. H. Hoveyda,  J. Am. Chem. Soc.  2012, 134, 12774-12779; (i) M. Yu, I. Ibrahem, M. Hasegawa, R. R. Schrock, A. H. Hoveyda,  J. Am. Chem. Soc.  2012, 134, 2788-2799). Although the ROCM of cyclobutenes to form racemic products has been demonstrated (see (a) M. L. Randall, J. A. Tallarico, M. L. Snapper,  J. Am. Chem. Soc.  1995, 117, 9610-9611; (b) M. L. Snapper, J. A. Tallarico, M. L. Randall,  J. Am. Chem. Soc.  1997, 119, 1478-1479; (c) J. A. Tallarico, M. L. Randall, M. L. Snapper,  Tetrahedron  1997, 53, 16511-16520; (d) T. O. Schrader, M. L. Snapper,  J. Am. Chem. Soc.  2002, 124, 10998-11000; (e) B. H. White, M. L. Snapper,  J. Am. Chem. Soc.  2003, 125, 14901-14904), previous studies of their AROCM reactions have afforded products with low enantioenrichment (see M. Yu, I. Ibrahem, M. Hasegawa, R. R. Schrock, A. H. Hoveyda,  J. Am. Chem. Soc.  2012, 134, 2788-2799). 
         [0008]    Despite the advances achieved in the art, a continuing need therefore exists for further improvements in the areas of Z-selective AROCM (see (a) Endo, K.; Grubbs, R. H.,  J. Am. Chem. Soc.  2011, 133, 8525-8527; (b) Keitz, B. K.; Endo, K.; Herbert, M. B.; Grubbs, R. H.,  J. Am. Chem. Soc.  2011, 133, 9686-9688; (c) Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H.,  J. Am. Chem. Soc.  2012, 134, 693-699; (d) Rosebrugh, L. E.; Herbert, M. B.; Marx, V. M.; Keitz, B. K.; Grubbs, R. H.,  J. Am. Chem. Soc.  2013, 135, 1276-1279). The present invention is directed to addressing one or more of those concerns. 
       SUMMARY 
       [0009]    The invention is directed to addressing one or more of the aforementioned concerns, and, in one embodiment, provides an enantioenriched C—H activated catalyst compound composed of a Group 8 transition metal complex and a chelating ligand structure formed from the metal center M, a neutral electron donor ligand L 1 , and a 2-electron anionic donor bridging moiety, Q*. A general structure of catalyst compounds according to the invention is shown below. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein, M is a Group 8 transition metal (e.g., Ru or Os); X 1  is an anionic ligand; L 1  is a neutral two electron ligand, where L 1  may connect with R 2 ; R 1  and R 2  are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, and wherein R 1  may connect with R 2  and/or L 1 ; Q*is a 2-electron anionic donor bridging moiety (e.g., alkyl, aryl, carboxylate, alkoxy, aryloxy, or sulfonate, etc.). 
         [0010]    We have discovered that enantiopure versions of these catalysts exhibit both high Z-selectivity and enantioselectivity in AROCM due to the rigidity imparted by the heterocyclic carbene-metal chelate. 
         [0011]    In summary, we have developed an enantioenriched ruthenium metathesis catalyst capable of highly Z-selective and enantioselective ROCM. An NHC ligand that chelates through a Ru—C bond is key to the design of the catalyst, which features a stereogenic Ru atom. The reaction is amenable to modification of both the α-olefin and norbornene component, which significantly broadens the scope of this methodology. 
         [0012]    Furthermore, the highly enantioselective synthesis of 1,2-anti diols was accomplished by the application of catalyst 4 to the AROCM of cis-dioxygenated cyclobutenes. The reaction is robust, tolerating modifications in reaction conditions and substitution on the reactants. Enantioenrichment of the major Z isomers was exceptionally high, ranging from 89-99% ee. The rapid synthesis of insect pheromone (+)-endo brevicomin was accomplished, affording the natural product in 95% ee. A 1,5-diene generated by the AROCM reaction was chemoselectively functionalized to afford ribose derivative 21, demonstrating the utility of the building blocks afforded by the title reaction. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0013]      FIG. 1  is a graph demonstrating the E/Z ratio versus conversion for the reaction leading to product 9e as described in the Examples. 
           [0014]      FIG. 2  depicts the X-ray crystal structure (ORTEP drawing) of complex 3 as described in the Examples. 
           [0015]      FIG. 3 . X-ray crystal structure (ORTEP drawing) of compound ent-S3 as described in the Examples. 
       
    
    
     DETAILED DESCRIPTION 
     Terminology and Definitions 
       [0016]    Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting. 
         [0017]    As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an α-olefin” includes a single α-olefin as well as a combination or mixture of two or more α-olefins, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like. 
         [0018]    As used in the specification and the appended claims, the terms “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion. 
         [0019]    In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings: 
         [0020]    The term “alkyl” as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms. The term “substituted alkyl” refers to alkyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively. 
         [0021]    The term “alkylene” as used herein refers to a difunctional linear, branched, or cyclic alkyl group, where “alkyl” is as defined above. 
         [0022]    The term “alkenyl” as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkenyl” intends an alkenyl group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic alkenyl group, preferably having 5 to 8 carbon atoms. The term “substituted alkenyl” refers to alkenyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively. 
         [0023]    The term “alkenylene” as used herein refers to a difunctional linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined above. 
         [0024]    The term “alkynyl” as used herein refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to alkynyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively. 
         [0025]    The term “alkoxy” as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as —O-alkyl where alkyl is as defined above. A “lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage. 
         [0026]    The term “aryl” as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups, and the terms “heteroatom-containing aryl” and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra. 
         [0027]    The term “aryloxy” as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above. An “aryloxy” group may be represented as —O-aryl where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like. 
         [0028]    The term “alkaryl” refers to an aryl group with an alkyl substituent, and the term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula —OR wherein R is alkaryl or aralkyl, respectively, as just defined. 
         [0029]    The term “acyl” refers to substituents having the formula —(CO)-alkyl, —(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers to substituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or —O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as defined above. 
         [0030]    The terms “cyclic” and “ring” refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic. 
         [0031]    The terms “halo” and “halogen” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent. 
         [0032]    “Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl” intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term “hydrocarbylene” intends a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term “lower hydrocarbylene” intends a hydrocarbylene group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbyl substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, “substituted hydrocarbylene” refers to hydrocarbylene substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbylene” and heterohydrocarbylene” refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively. 
         [0033]    The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is heteroatom-containing, the terms “heteroaryl” and heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like. It should be noted that a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.” Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom-containing alicyclic groups are pyrrolidino, morpholino, piperazino, piperidino, etc. 
         [0034]    By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C 1 -C 24  alkoxy, C 2 -C 24  alkenyloxy, C 2 -C 24  alkynyloxy, C 5 -C 24  aryloxy, C 6 -C 24  aralkyloxy, C 6 -C 24  alkaryloxy, acyl (including C 2 -C 24  alkylcarbonyl (—CO-alkyl) and C 6 -C 24  arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C 2 -C 24  alkylcarbonyloxy (—O—CO-alkyl) and C 6 -C 24  arylcarbonyloxy (—O—CO-aryl)), C 2 -C 24  alkoxycarbonyl (—(CO)—O-alkyl), C 6 -C 24  aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X is halo), C 2 -C 24  alkylcarbonato (—O—(CO)—O-alkyl), C 6 -C 24  arylcarbonato (—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO − , carbamoyl (—(CO)—NH 2 ), mono-(C 1 -C 24  alkyl)-substituted carbamoyl (—(CO)—NH(C 1 -C 24  alkyl)), di-(C 1 -C 24  alkyl)-substituted carbamoyl (—(CO)—N(C 1 -C 24  alkyl) 2 ), mono-(C 1 -C 24  haloalkyl)-substituted carbamoyl (—(CO)—NH(C 1 -C 24  alkyl)), di-(C 1 -C 24  haloalkyl)-substituted carbamoyl (—(CO)—N(C 1 -C 24  alkyl) 2 ), mono-(C 5 -C 24  aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C 5 -C 24  aryl)-substituted carbamoyl (—(CO)—N(C 5 -C 24  aryl) 2 ), di-N—(C 1 -C 24  alkyl), N—(C 5 -C 24  aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH 2 ), mono-(C 1 -C 24  alkyl)-substituted thiocarbamoyl (—(CO)—NH(C 1 -C 24  alkyl)), di-(C 1 -C 24  alkyl)-substituted thiocarbamoyl (—(CO)—N(C 1 -C 24  alkyl) 2 ), mono-(C 5 -C 24  aryl)-substituted thiocarbamoyl (—(CO)—NH-aryl), di-(C 5 -C 24  aryl)-substituted thiocarbamoyl (—(CO)—N(C 5 -C 24  aryl) 2 ), di-N—(C 1 -C 24  alkyl), N—(C 5 -C 24  aryl)-substituted thiocarbamoyl, carbamido (—NH—(CO)—NH 2 ), cyano(—C═N), cyanato (—O—C═N), thiocyanato (—S—C═N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH 2 ), mono-(C 1 -C 24  alkyl)-substituted amino, di-(C 1 -C 24  alkyl)-substituted amino, mono-(C 5 -C 24  aryl)-substituted amino, di-(C 5 -C 24  aryl)-substituted amino, C 2 -C 24  alkylamido (—NH—(CO)-alkyl), C 6 -C 24  arylamido (—NH—(CO)-aryl), imino (—CR═NH where R=hydrogen, C 1 -C 24  alkyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), C 2 -C 20  alkylimino (—CR═N(alkyl), where R=hydrogen, C 1 -C 24  alkyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), arylimino (—CR═N(aryl), where R=hydrogen, C 1 -C 20  alkyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), nitro (—NO 2 ), nitroso (—NO), sulfo (—SO 2 —OH), sulfonato (—SO 2 —O − ), C 1 -C 24  alkylsulfanyl (—S-alkyl; also termed “alkylthio”), C 5 -C 24  arylsulfanyl (—S-aryl; also termed “arylthio”), C 1 -C 24  alkylsulfinyl (—(SO)-alkyl), C 5 -C 24  arylsulfinyl (—(SO)-aryl), C 1 -C 24  alkylsulfonyl (—SO 2 -alkyl), C 1 -C 24  monoalkylaminosulfonyl —SO 2 —N(H) alkyl), C 1 -C 24  dialkylaminosulfonyl —SO 2 —N(alkyl) 2 , C 5 -C 24  arylsulfonyl (—SO 2 -aryl), boryl (—BH 2 ), borono (—B(OH) 2 ), boronato (—B(OR) 2  where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH) 2 ), phosphonato (—P(O)(O − ) 2 ), phosphinato (—P(O)(O − )), phospho (—PO 2 ), and phosphino (—PH 2 ); and the hydrocarbyl moieties C 1 -C 24  alkyl (preferably C 1 -C 12  alkyl, more preferably C 1 -C 6  alkyl), C 2 -C 24  alkenyl (preferably C 2 -C 12  alkenyl, more preferably C 2 -C 6  alkenyl), C 2 -C 24  alkynyl (preferably C 2 -C 12  alkynyl, more preferably C 2 -C 6  alkynyl), C 5 -C 24  aryl (preferably C 5 -C 14  aryl), C 6 -C 24  alkaryl (preferably C 6 -C 16  alkaryl), and C 6 -C 24  aralkyl (preferably C 6 -C 16  aralkyl). 
         [0035]    By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove. The term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface. 
         [0036]    In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above. Analogously, the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated. 
         [0037]    “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present. 
         [0038]    The term enantioenriched C—H activated catalyst refers to mirror images when one chiral center is present and diastereomers with 2 or more chiral centers are present. 
       Catalyst Complexes 
       [0039]    In general, the catalyst complexes of the invention comprise a Group 8 metal (M), an alkylidene moiety (═CR 1 R 2 ), or more generally (═(C) m CR 1 R 2 ), an anionic ligand (X 1 ), a neutral ligand (L 1 ) and a heterocyclic carbene ligand that is linked to the metal via a 2-electron anionic donor bridging moiety (Q*). The olefin metathesis catalyst complex is preferably a Group 8 transition metal complex having the structure of formula (II) 
         [0000]    
       
                 
         
             
             
         
       
     
         [0040]    in which: 
         [0041]    L 1  is a neutral electron donor ligand; 
         [0042]    Q* is a 2-electron anionic donor bridging moiety linking R 3  and Ru; and may be hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and/or heteroatom-containing alkylene) or —(CO)—; 
         [0043]    Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Q is often, although again not necessarily, a two-atom linkage or a three-atom linkage; 
         [0044]    X is an atom selected from C, N, O, S, and P. Since O and S are divalent, n is necessarily zero when X is O or S. Similarly, when X is N or P, then n is 1, and when X is C, then n is 2; 
         [0045]    R 1  and R 2  are independently selected from hydrogen, hydrocarbyl (e.g., C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl (e.g., substituted heteroatom-containing C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), and functional groups. R 1  and R 2  may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and/or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ring atoms. 
         [0046]    R 3  and R 4  are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing, hydrocarbyl (e.g., C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl (e.g., substituted heteroatom-containing C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), and functional groups. 
         [0047]    X 1  is a bidentate anionic ligand. Typically, X 1  is nitrate, C 1 -C 20  alkylcarboxylate, C 6 -C 24  arylcarboxylate, C 2 -C 24  acyloxy, C 1 -C 20  alkylsulfonato, C 5 -C 24  arylsulfonato, C 1 -C 20  alkylsulfanyl, C 5 -C 24  arylsulfanyl, C 1 -C 20  alkylsulfinyl, or C 5 -C 24  arylsulfinyl. In some embodiments, X 1  is benzoate, pivalate, or nitrate. More specifically, X 1  may be is CF 3 CO 2 , CH 3 CO 2 , CH 3 CH 2 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO 2 , (CH 3 ) 2 CHCO 2 , (CF 3 ) 2 (CH 3 )CO 2 , (CF 3 )(CH 3 ) 2 CO 2 , benzoate, naphthylate, tosylate, mesylate, or trifluoromethane-sulfonate. In one more preferred embodiment, X 1  is nitrate (NO 3   − ). 
         [0048]    In certain catalysts, R 1  is hydrogen and R 2  is selected from C 1 -C 20  alkyl, C 2 -C 20  alkenyl, and C 5 -C 24  aryl, more preferably C 1 -C 6  alkyl, C 2 -C 6  alkenyl, and C 5 -C 14  aryl. Still more preferably, R 2  is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, and phenyl. Most preferably, R 2  is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. More specifically, R 2  may be phenyl or —C═C(CH 3 ) 2 . 
         [0049]    Any two or more (typically two, three, or four) of X 1 , L 1 , R 1 , and R 2  can be taken together to form a cyclic group, including bidentate or multidentate ligands, as disclosed, for example, in U.S. Pat. No. 5,312,940 to Grubbs et al. When any of X 1 , L 1 , R 1 , and R 2  are linked to form cyclic groups, those cyclic groups may contain 4 to 12, preferably 4, 5, 6, 7 or 8 atoms, or may comprise two or three of such rings, which may be either fused or linked. 
         [0050]    In particular embodiments, Q is a two-atom linkage having the structure —CR 11 R 12 —CR 13 R 14 — or —CR 11 ═CR 13 —, preferably —CR 11 R 12 —CR 13 R 14 —, wherein R 11 , R 12 , R 13 , and R 14  are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of suitable functional groups include carboxyl, C 1 -C 20  alkoxy, C 5 -C 24  aryloxy, C 2 -C 20  alkoxycarbonyl, C 5 -C 24  alkoxycarbonyl, C 2 -C 24  acyloxy, C 1 -C 20  alkylthio, C 5 -C 24  arylthio, C 1 -C 20  alkylsulfonyl, and C 1 -C 20  alkylsulfinyl, optionally substituted with one or more moieties selected from C 1 -C 12  alkyl, C 1 -C 12  alkoxy, C 5 -C 14  aryl, hydroxyl, sulfhydryl, formyl, and halide. R 11 , R 12 , R 13 , and R 14  are preferably independently selected from hydrogen, C 1 -C 12  alkyl, substituted C 1 -C 12  alkyl, C 1 -C 12  heteroalkyl, substituted C 1 -C 12  heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two of R 11 , R 12 , R 13 , and R 14  may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C 4 -C 12  alicyclic group or a C 5  or C 6  aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents. In one further aspect, any one or more of R 11 , R 12 , R 13 , and R 14  comprises one or more of the linkers. 
         [0051]    In more particular aspects, R 3  and R 4  maybe alkyl or aryl, and may be independently selected from alkyl, aryl, cycloalkyl, heteroalkyl, alkenyl, alkynyl, and halo or halogen-containing groups. More specifically, R 3  and R 4  may be independently selected from C 1 -C 20  alkyl, C 5 -C 14  cycloalkyl, C 1 -C 20  heteroalkyl, or halide. Suitable alkyl groups include, without limitation, methyl, ethyl, n-propyl, isopropyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like; suitable cycloalkyl groups include cyclopentyl, cyclohexyl, adamantyl, pinenyl, terpenes and terpenoid derivatives and the like; suitable alkenyl groups include ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like; suitable alkynyl groups include ethynyl, n-propynyl, and the like. 
         [0052]    When R 3  or R 4  are aromatic, each can be independently composed of one or two aromatic rings, which may or may not be substituted, e.g., R 3  and R 4  may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like. In a particular embodiment, R 3  and R 4  are independently an unsubstituted phenyl or phenyl substituted with up to three substituents selected from C 1 -C 20  alkyl, C 1 -C 20  alkylcarboxylate, substituted C 1 -C 20  alkyl, C 1 -C 20  heteroalkyl, substituted C 1 -C 20  heteroalkyl, C 5 -C 24  aryl, substituted C 5 -C 24  aryl, C 5 -C 24  heteroaryl, C 6 -C 24  aralkyl, C 6 -C 24  alkaryl, or halide. Preferably, any substituents present are hydrogen C 1 -C 12  alkyl, C 1 -C 12  alkoxy, C 5 -C 14  aryl, substituted, C 5 -C 14  aryl, or halide. More particularly, R 3  and R 4  may be independently substituted with hydrogen, C 1 -C 4  alkyl, C 1 -C 4  alkylcarboxylate, C 1 -C 4  alkoxy, C 5 -C 14  aryl, substituted C 5 -C 14  aryl, or halide. As an example, R 3  and R 4  are selected from cyclopentyl, cyclohexyl, adamantyl, norbonenyl, pinenyl, terpenes and terpenoid derivatives, mesityl, diisopropylphenyl or, more generally, cycloalkyl substituted with one, two or three C 1 -C 4  alkyl or C 1 -C 4  alkoxy groups, or a combination thereof. 
         [0053]    Particular complexes wherein R 2  and L 1  are linked to form a chelating carbene ligand are examples of another group of catalysts, and are commonly called “Grubbs-Hoveyda” catalysts. Grubbs-Hoveyda metathesis-active metal carbene complexes of the invention may be described by the formula VIII. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0054]    wherein, 
         [0055]    X 1 , Q, Q*, R 3  and R 4  are as previously defined herein; 
         [0056]    Y is a heteroatom selected from N, O, S, and P; preferably Y is O or N; 
         [0057]    R 5 , R 6 , R 7 , and R 8  are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, wherein any combination of R 5 , R 6 , R 7 , and R 8  can be linked to form one or more cyclic groups;
       n is 1 or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and       
 
         [0059]    Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein any combination or combinations of X 1 , Q*, Y, Z, R 5 , R 6 , R 7 , and R 8  are linked to a support. 
       Strained Olefin Reactant 
       [0060]    The AROCM reaction catalyzed by the complexes described above involve a strained olefin reactant and a second α-olefin reactant, wherein the two reactants are brought into contact in the presence of a catalytically effective amount of the complex, under conditions and for a time period effective to allow the AROCM reaction to occur. In general, the strained olefin reactant may be represented by the structure of formula (XIII): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein J and R 13  are as follows: 
         [0061]    R 13  is selected from the group consisting of hydrogen, hydrocarbyl (e.g., C 1 -C 20  alkyl, C 5 -C 20  aryl, C 5 -C 30  aralkyl, or C 5 -C 30  alkaryl), substituted hydrocarbyl (e.g., substituted C 1 -C 20  alkyl, C 5 -C 20  aryl, C 5 -C 30  aralkyl, or C 5 -C 30  alkaryl), heteroatom-containing hydrocarbyl (e.g., C 1 -C 20  heteroalkyl, C 5 -C 20  heteroaryl, heteroatom-containing C 5 -C 30  aralkyl, or heteroatom-containing C 5 -C 30  alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C 1 -C 20  heteroalkyl, C 5 -C 20  heteroaryl, heteroatom-containing C 5 -C 30  aralkyl, or heteroatom-containing C 5 -C 30  alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (“Fn”) such as phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C 1 -C 20  alkylsulfanyl, C 5 -C 20  arylsulfanyl, C 1 -C 20  alkylsulfonyl, C 5 -C 20  arylsulfonyl, C 1 -C 20  alkylsulfinyl, C 5 -C 20  arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C 1 -C 20  alkoxy, C 5 -C 20  aryloxy, C 2 -C 20  alkoxycarbonyl, C 5 -C 20  aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C 1 -C 20  thioester, cyano, cyanato, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or Ge). R 13  may itself be one of the aforementioned groups, such that the Fn moiety is directly bound to the olefinic carbon atom indicated in the structure. In the latter case, however, the functional group will generally not be directly bound to the olefinic carbon through a heteroatom containing one or more lone pairs of electrons, e.g., an oxygen, sulfur, nitrogen or phosphorus atom, or through an electron-rich metal or metalloid such as Ge, Sn, As, Sb, Se, Te, etc. With such functional groups, there will normally be an intervening linkage Z, such that R 13  then has the structure —(Z) n -Fn wherein n is 1, Fn is the functional group, and Z is a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage. 
         [0062]    J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linkage, wherein when J is substituted hydrocarbylene or substituted heteroatom-containing hydrocarbylene, the substituents may include one or more —(Z) n —Fn groups, wherein n is zero or 1, and Fn and Z are as defined previously. Additionally, two or more substituents attached to ring carbon (or other) atoms within J may be linked to form a bicyclic or polycyclic olefin. J will generally contain in the range of approximately 4 to 14 ring atoms, typically 4 to 8 ring atoms, for a monocyclic olefin, and, for bicyclic and polycyclic olefins, each ring will generally contain 4 to 8, typically 5 to 7, ring atoms. 
         [0063]    Mono-unsaturated cyclic olefin reactants encompassed by structure (XII) may be represented by the structure (XIV): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein b is an integer generally although not necessarily in the range of 0 to 10, typically 0 to 5, R 13  is as defined above, and R 14 , R 15 , R 16 , R 17 , R 18 , and R 19  are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and —(Z) n -Fn where n, Z and Fn are as defined previously, and wherein if any of the R 14  through R 19  moieties is substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, the substituents may include one or more —(Z) n -Fn groups. Accordingly, R 14 , R 15 , R 16 , R 17 , R 18 , and R 19  may be, for example, hydrogen, hydroxyl, C 1 -C 20  alkyl, C 5 -C 20  aryl, C 1 -C 20  alkoxy, C 5 -C 20  aryloxy, C 2 -C 20  alkoxycarbonyl, C 5 -C 20  aryloxycarbonyl, amino, amido, nitro, etc. Furthermore, any of the R 14  through R 19  moieties can be linked to any other of the R 14  through R 19  moieties to provide a bicyclic or polycyclic olefin, and the linkage may include heteroatoms or functional groups, e.g., the linkage may include an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. 
         [0064]    Examples of monounsaturated, monocyclic olefins encompassed by structure (XIV) include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions thereof such as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 1-methylcyclopentene, 4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, etc. 
         [0065]    Monocyclic diene reactants encompassed by structure (XIII) may be generally represented by the structure (XV): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein c and d are independently integers in the range of 1 to about 8, typically 2 to 4, preferably 2 (such that the reactant is a cyclooctadiene), R 13  is as defined above, and R 20 , R 21 , R 22 , R 23 , R 24  and R 25  are defined as for R 14  through R 19 . In this case, it is preferred that R 24  and R 25  be nonhydrogen substituents, in which case the second olefinic moiety is tetrasubstituted, so that the ROCM reaction proceeds selectively at only one of the two olefin functionalities. Examples of monocyclic diene reactants include, without limitation, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and substituted analogs thereof. Triene reactants are analogous to the diene structure (XV), and will generally contain at least one methylene linkage between any two olefinic segments. 
         [0066]    Bicyclic and polycyclic olefinic reactants encompassed by structure (XII) may be generally represented by the structure (XVI) 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein e is an integer in the range of 1 to 8, typically 2 to 4, f is generally 1 or 2, T is lower alkylene or lower alkenylene, generally substituted or unsubstituted methyl or ethyl, R 13  is as defined above, and R 27 , R 28 , R 29 , and R 30  are as defined for R 14  through R 19 . Preferred olefinic reactants within this group are in the norbornene family, having the structure (XVII) 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein R 13 , and R 27  through R 30  are as defined previously, and R 28A  and R 29A  are defined as for R 28  and R 29 . 
         [0067]    Examples of bicyclic and polycyclic olefinic reactants thus include, without limitation, dicyclopentadiene, tricyclopentadiene, dicyclohexadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-acetylnorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxy-carbonylnorbornene, 5-cyanonorbornene, 5,5,6-trimethyl-2-norbornene, cyclo-hexenylnorbornene, endo, exo-5,6-dimethoxynorbornene, endo, endo-5,6-dimethoxynorbornene, endo,exo-5,6-dimethoxycarbonyl-norbornene, endo, endo-5,6-dimethoxycarbonylnorbornene, 2,3-dimethoxynorbornene, norbornadiene, tricycloundecene, tetracyclododecene, 8-methyltetracyclododecene, 8-ethyl-tetracyclododecene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclo-dodecene, 8-cyanotetracyclododecene, pentacyclopentadecene, pentacyclohexadecene, 1,9-octadecadiene, and the like. 
       α-Olefin Reactant 
       [0068]    In general, the α-olefin reactant may be represented by the structure of formula (XVIII): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein Y α  is selected from the group comprising nil, CH 2 , O, or S and R α  is selected from the group consisting of hydrogen, hydrocarbyl (e.g., C 1 -C 20  alkyl, C 5 -C 20  aryl, C 5 -C 30  aralkyl, or C 5 -C 30  alkaryl), substituted hydrocarbyl (e.g., substituted C 1 -C 20  alkyl, C 5 -C 20  aryl, C 5 -C 30  aralkyl, or C 5 -C 30  alkaryl), heteroatom-containing hydrocarbyl (e.g., C 1 -C 20  heteroalkyl, C 5 -C 20  heteroaryl, heteroatom-containing C 5 -C 30  aralkyl, or heteroatom-containing C 5 -C 30  alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C 1 -C 20  heteroalkyl, C 5 -C 20  heteroaryl, heteroatom-containing C 5 -C 30  aralkyl, or heteroatom-containing C 5 -C 30  alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (“Fn”) such as phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C 1 -C 20  alkylsulfanyl, C 5 -C 20  arylsulfanyl, C 1 -C 20  alkylsulfonyl, C 5 -C 20  arylsulfonyl, C 1 -C 20  alkylsulfinyl, C 5 -C 20  arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C 1 -C 20  alkoxy, C 5 -C 20  aryloxy, C 2 -C 20  alkoxycarbonyl, C 5 -C 20  aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C 1 -C 20  thioester, cyano, cyanato, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or Ge). 
       Catalyzed Asymmetric Ring Opening/Cross Metathesis of Bicyclic Olefins and α-Olefins 
       [0069]    We anticipated that enantiopure versions of the newly developed catalysts would exhibit high Z-selectivity and enantioselectivity in AROCM due to the rigidity imparted by the Ru—C chelate. Herein we report a new homochiral stereogenic-at-ruthenium complex that exhibits high enantioselectivity in the AROCM of norbornene derivatives. 
         [0070]    Enantioenriched 4 was synthesized by resolution as shown in Scheme 1. Treatment of racemic iodide 1 (see Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H.,  J. Am. Chem. Soc.  2012, 134, 693-699) with silver carboxylate 2 cleanly formed a 1:1 mixture of diastereomers in 97% yield. Chromatographic separation of the mixture afforded a 45% yield (90% of theoretical maximum) of 3 (&gt;95:5 dr). The absolute stereochemistry of complex 3 was confirmed by X-ray crystallography ( FIG. 2 ). Sequential treatment of carboxylate 3 with para-toluenesulfonic acid and sodium nitrate produced the enantioenriched nitrate complex 4 in 43% yield. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0071]    While complex 3 exhibited low enantioselectivity in AROCM, 1 mol % of complex 4 catalyzed the reaction of norbornene 5 with an excess of allyl acetate (6) to produce a 64% yield of diene (1S,2R,3S,4R)-7 with 95% Z-selectivity and 93% ee (Scheme 2) (Absolute configurations were assigned by analogy to that of 9c, which was determined by X-ray crystallography). The highly selective reaction produces four contiguous stereocenters on a tetra-substituted cyclopentane ring. Optimization of the process revealed that 7 equiv. of α-olefin, 1 mol % catalyst loading at 23° C. and 0.5 M concentration in THF afforded the highest yield and selectivity. Ethereal solvents were optimal, with catalyst solubility improved in THF over diethyl ether. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0072]    In order to demonstrate the scope of Z-selective catalyst 4, a variety of α-olefins bearing diverse functionality were employed in order to determine their effect on the efficiency and enantioselectivity of the reaction. As illustrated in Table 1, replacing allyl acetate with N-Boc-allylamine provided amine-containing product 8a in equally high enantioselectivity (94% ee). Utilizing an olefin bearing a remote ester did not impact the Z-selectivity and afforded 8b in 91% ee. 
         [0000]    
       
         
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 AROCM with Different α-Olefin Partners a   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
             
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   a Yields correspond to isolated product; Z/E ratios determined by 500 MHz  1 H NMR of the crude reaction mixture; ee of pure products measured with chiral SFC. 
               
             
          
         
       
     
         [0073]    Bulkier allylic substituents such as para-methoxy phenyl and pinacol boronic ester gave products 8c and 8d with moderate enantioselectivity (81% and 75% ee, respectively). A simple α-olefin such as 1-hexene also gave good yield, Z-selectivity, and enantioselectivity (8e, 89% ee), demonstrating that allylic functionality is not required to confer a selective reaction. The examples in Table 1 suggest that catalyst 4 is capable of producing a range of AROCM products (Attempts to employ heteroatom-substituted olefins (butyl vinyl ether) resulted in no ROCM product, presumably due to catalyst deactivation). 
         [0074]    The norbornene component was then altered to understand its impact on Z-selectivity and enantioselectivity. As a basis for comparison, the substrates were treated with 7 equivalents of allyl acetate under the optimized catalytic conditions. Norbornenes bearing coordinating functionality such as acetate (to form 9a) and N-phenyl succinimide (to form 9b) resulted in reduced yield and slower reaction, respectively. The dimethyl substituted anhydride afforded a 65% yield of 9d, which contains two vicinal all-carbon quaternary stereocenters, demonstrating the power of AROCM to afford otherwise synthetically challenging products in high ee (95%). Aryl ether 9e was produced in 95% ee, although interestingly as a 7:3 Z/E mixture. The results in Table 2 support the observation that substrates bearing 2,3-endo substitution react with high Z-selectivity; substrates lacking this substitution pattern show reduced diastereoselectivity. 
         [0000]    
       
         
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                 Influence of Strained Olefin Reactant a   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
             
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   a Yields correspond to isolated product; Z/E ratios determined by GC; ee of pure products measured with chiral SFC. 
               
               
                   b  Conducted at 3 mol % catalyst loading for 5 h. 
               
             
          
         
       
     
         [0075]    The fact that Z-9e and E-9e are formed in identical enantioenrichment has important mechanistic implications and offers indirect evidence of the active catalytic species. The result suggests that the enantiodetermining step most likely precedes the olefin geometry-determining step (This assumes that secondary metathesis processes proceed at a negligible rate compared to the productive (ROCM) reaction. Measurements of the formation of 9e (see Experimental) show that the Z/E ratio is constant during the course of the reaction and for several hours after complete conversion). This conclusion requires the initial enantiodetermining ring-opening event to occur with a ruthenium methylidene (Scheme 3). Subsequent cross metathesis of the ring-opened product bearing a ruthenium alkylidene with an equivalent of α-olefin would then produce the observed product. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0076]    On the basis of this indirect mechanistic evidence and the absolute configuration of the isolated product, we propose that the methylidene shown in Scheme 3 initially reacts with the norbornene component in an enantioselective ring-opening event. It is hypothesized that the enantioselectivity is governed by approach of the methylidene to the less-hindered exo face while the mesityl “cap” forces the bulk of the norbornene component to orient away from the NHC ligand (see Liu, P.; Xu, X.; Dong, X.; Keitz, B. K.; Herbert, M. B.; Grubbs, R. H.; Houk, K. N.,  J. Am. Chem. Soc.  2012, 134, 1464-1467). The proposed methylidene is most likely produced by initial cross metathesis of 4 with a molecule of α-olefin, resulting in epimerization at the ruthenium center. 
       Catalyzed Asymmetric Ring Opening/Cross Metathesis of Monocyclic Olefins and α-Olefins 
       [0077]    It was envisioned that the desymmetrization of suitably substituted meso cyclobutenes in AROCM would afford the 1,2-anti diol motif in perfect anti diastereoselectivity and potentially high enantioselectivity upon application of a newly developed cyclometalated metathesis catalyst 4 (Scheme 4) (see J. Hartung, R. H. Grubbs,  J. Am. Chem. Soc.  2013, 135, 10183-10185). The resultant 1,5-diene would be a versatile synthetic intermediate due to the differential reactivity of the two alkenes, paving the way for further chemoselective transformations. Herein, we report the successful application of 4 to afford highly enantioenriched 1,2-anti diols and demonstrate the versatility of these products in the synthesis of the insect pheromone (+)-endo brevicomin and a derivative of the monosaccharide L-ribose. Pest control strategies utilizing insect pheromones have become a promising alternative to the application of broad-spectrum insecticides, underscoring the importance of rapid synthetic routes to (+)-endo brevicomin and related bioactive compounds (see (a) P. E. Howse, I. D. R. Stevens,  Insect Pheromones and their Use in Pest Management , Chapman &amp; Hall, New York, 1998; (b) Recent work from this group has demonstrated the application of racemic 4 to the synthesis of Lepidoptera female sex pheromones, see M. B. Herbert, V. M. Marx, R. L. Pederson, R. H. Grubbs,  Angew. Chem.  2013, 125, 328-332 ; Angew. Chem., Int. Ed.  2013, 52, 310-314). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0078]    Initial attempts to form 1,2-anti diols were carried out with complex 4, allyl acetate (11), and cis-3,4-dibenzyloxycyclobutene (10, Table 3), which was synthesized by substitution of commercially available cis-3,4-dichlorocyclobutene with sodium phenylmethanolate (see W. Kirmse, F. Scheidt, H. J. Vater,  J. Am. Chem. Soc.  1978, 100, 3945-3946). Solvent had no effect on selectivity of the AROCM reaction except for slightly diminished enantioselectivity in CH 2 Cl 2  (entry 1, Table 3); yield was highest in THF (entry 4, Table 3). The effect of stoichiometry in AROCM has been explored for a number of catalysts (see (a) J. M. Berlin, S. D. Goldberg, R. H. Grubbs,  Angew. Chem.  2006, 118, 7753-7757 ; Angew. Chem., Int. Ed.  2006, 45, 7591-7595; (b) M. Yu, I. Ibrahem, M. Hasegawa, R. R. Schrock, A. H. Hoveyda,  J. Am. Chem. Soc.  2012, 134, 2788-2799; (c) D. S. La, J. G. Ford, E. S. Sattely, P. J. Bonitatebus, R. R. Schrock, A. H. Hoveyda,  J. Am. Chem. Soc.  1999, 121, 11603-11604). In the current study, an excess of terminal olefin was optimal (7 equiv, entry 4, Table 3); as the equivalents of terminal olefin were reduced, the yield of the reaction dropped, yet a modest yield of 29% could be obtained with 1.2 equivalents of 11. No di-cross products were observed. Reducing the concentration also resulted in lower yield, leading to the optimal conditions of 7 equiv. of terminal olefin 11 in THF at a concentration of 0.5 M in 10 with 1 mol % 4 for 1.5 h. It is worth noting that although alternative solvents or stoichiometry negatively impacted reaction efficiency, the diastereo- and enantioselectivity remained consistently high, demonstrating the robustness of the reaction. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Optimization of the AROCM of Cyclobutene 10 with 11. 
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
           
               
                   
                   
                 Conc 
                   
                   
                   
                 ee 
               
               
                 entry 
                 Equiv 11 
                 (M) 
                 Solvent 
                 Yield [a]   
                 % Z [a]   
                 (Z) [b]   
               
               
                   
               
             
          
           
               
                 1 
                 7 
                 0.5 
                 CH 2 Cl 2   
                 35 
                 83 
                 93 
               
               
                 2 
                 7 
                 0.5 
                 Benzene 
                 49 
                 84 
                 95 
               
               
                 3 
                 7 
                 0.5 
                 Toluene 
                 52 
                 84 
                 95 
               
               
                 4 
                 7 
                 0.5 
                 THF 
                 79 
                 85 
                 95 
               
               
                 5 
                 5 
                 0.5 
                 THF 
                 71 
                 84 
                 96 
               
               
                 6 
                 3 
                 0.5 
                 THF 
                 63 
                 85 
                 96 
               
               
                 7 
                 1.2 
                 0.5 
                 THF 
                 29 
                 87 
                 97 
               
               
                 8 
                 7 
                 0.3 
                 THF 
                 72 
                 85 
                 95 
               
               
                 9 
                 7 
                 0.1 
                 THF 
                 43 
                 85 
                 95 
               
               
                   
               
               
                   [a] Determined by GC. 
               
               
                   [b] Determined by chiral SFC. 
               
             
          
         
       
     
         [0079]    While the synthesis of a 1,2-anti alkoxy motif had been demonstrated, inclusion of alternative protecting groups on the diol motif strengthens the synthetic protocol. These modifications would allow a synthetic sequence to be designed taking into account the feasibility of removing the protecting groups in the presence of other functionality. Moreover, modulation of the size and electronics of the groups on the cyclobutene and terminal olefin reactants would provide a better understanding of the factors contributing to selectivity. 
         [0080]    A complement of commonly used hydroxyl protecting groups were tolerated on the cyclobutene and terminal olefin reactants, but enantio- and diastereoselectivity were affected by the choice of substituents (Tables 4 and 5) (Attempts to use cyclic protecting groups (ex: benzylidene acetal) resulted in low conversion). The increased bulkiness of the tert-butyldimethylsilyl ether resulted in improved Z selectivity and remarkable enantioselectivity (88% Z, 99% ee, 15a, Table 4), while hydroxyls and benzoates on the cyclobutene reactant led to Z products with 91% and 96% ee, respectively. The same enantioinduction was observed in products 15a and 15b. Isopropoxy substituents on the cyclobutene resulted in abrogation of catalyst activity presumably due to the formation of a stable chelating complex (In preliminary stoichiometric experiments with 4 and 13c, we observe the formation of a kinetically stable intermediate analogous to one described in a recent report on an enantiopure ruthenium alkylidene complex, see R. K. M. Khan, A. R. Zhugralin, S. Torker, R. V. O&#39;Brien, P. J. Lombardi, A. H. Hoveyda,  J. Am. Chem. Soc.  2012, 134, 12438-12441). 
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Scope of the AROCM Reaction with respect to Cyclobutene Substitution. [a]   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
           
               
                   
                   
                   
                   
                 % 
                 ee Z [d]   
               
               
                 R 1   
                 R 2   
                 Product 
                 Yield [b]   
                 Z [c]   
                 (ee E) [d]   
               
               
                   
               
               
                 TBS 
                 OH 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 66 
                 88 
                 99 (nd) 
               
               
                   
               
               
                 H 
                 OBz 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 67 
                 75 
                 91 (67) 
               
               
                   
               
               
                 Bz 
                 OH 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 69 
                 75 
                 96 (82) 
               
               
                   
               
               
                   i Pr 
                 OBz 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 &lt;5 
                 nd 
                 nd 
               
               
                   
               
               
                   [a] 0.1 mmol cyclobutene, 0.7 mmol terminal olefin. 
               
               
                   [b] Combined isolated yield of E and Z products. 
               
               
                   [c] Determined by 500 MHz  1 H NMR analysis of crude reaction mixture. 
               
               
                   [d] Determined by chiral SFC. 
               
             
          
         
       
     
         [0081]    High enantioselectivities were obtained with a wide range of terminal olefins. Among the 0-protecting groups surveyed (Table 5, 15e-h), the tert-butyldimethylsilyl group resulted in high enantioselectivity (89% ee, 15g), but the more electron-withdrawing benzoate ester was optimal, resulting in the highest enantioselectivity (97% ee, 15f). Terminal olefins bearing alkyl substitution resulted in higher diastereoselectivity and yield with similar levels of enantioselectivity (15i, 15j). The chiral allylation reagent 15k was synthesized in 91% ee, affording a functionally useful building block. Z and E isomers were isolable from each other by flash or thin layer chromatography in all cases except 15i. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Scope of the AROCM Reaction with respect to Terminal Olefin [a]   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
           
               
                   
                   
                   
                   
                 ee Z [d]   
               
               
                 R 2   
                 Product 
                 Yield [b]   
                 % Z [c]   
                 (ee E) [d]   
               
               
                   
               
               
                 OH 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 62 
                 89 
                 93 (86) 
               
               
                   
               
               
                 OBz 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 61 
                 88 
                 97 (88) 
               
               
                   
               
               
                 OTBS 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                      68 [e]   
                 87 
                 89 (77) 
               
               
                   
               
               
                 OBn 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 64 
                 86 
                 91 (nd) 
               
               
                   
               
               
                 4-MeOPh 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 76 
                 90 
                 93 (79) 
               
               
                   
               
               
                 CH 2 C(O)CH 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 65 
                 90 
                 92 (84) 
               
               
                   
               
               
                 BPin 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 50 
                      nd [f]   
                 91 (nd) 
               
               
                   
               
               
                   [a] 0.1 mmol cyclobutene, 0.7 mmol terminal olefin. 
               
               
                   [b] Combined isolated yield of E and Z products. 
               
               
                   [c] Determined by 500 MHz  1 H NMR analysis of crude reaction mixture. 
               
               
                   [d] Determined by chiral SFC. 
               
               
                   [e] Yield determined after derivatization to 15e. 
               
               
                   [f] Not determined due to instability of E product. 
               
             
          
         
       
     
         [0082]    We next explored the synthetic utility of the 1,2-anti diol fragments produced in the AROCM reaction. Cyclic ketals derived from the 1,2-anti diol motif feature prominently in the structures of several natural products (see (a) R. M. Silverstein, R. G. Brownlee, T. E. Bellas, D. L. Wood, L. E. Browne,  Science  1968, 159, 889-891; (b) T. Yasumoto, M. Murata, Y. Oshima, M. Sano, G. K. Matsumoto, J. Clardy,  Tetrahedron  1985, 41, 1019-1025; (c) D. Uemura, T. Chou, T. Haino, A. Nagatsu, S. Fukuzawa, S. Z. Zheng, H. S. Chen,  J. Am. Chem. Soc.  1995, 117, 1155-1156; (d) T. Chou, O. Kamo, D. Uemura,  Tetrahedron Lett.  1996, 37, 4023-4026; (e) T. Chou, T. Haino, M. Kuramoto, D. Uemura,  Tetrahedron Lett.  1996, 37, 4027-4030). Accordingly, we targeted this structure in the context of a synthesis of the insect pheromone (+)-endo brevicomin (19, Scheme 5) (For catalytic asymmetric syntheses, see (a) A. C. Oehlschlager, B. D. Johnston,  J. Org. Chem.  1987, 52, 940-943; (b) S. D. Burke, N. Muller, C. M. Beaudry,  Org. Lett.  1999, 1, 1827-1829; (c) S.-G. Kim, T.-H. Park, B. J. Kim,  Tetrahedron Lett.  2006, 47, 6369-6372; (d) S. Singh, P. J. Guiry,  J. Org. Chem.  2009, 74, 5758-5761; for syntheses relying on stoichiometric chiral reagents, see (e) R. Bernardi, C. Fuganti, P. Grasselli,  Tetrahedron Lett.  1981, 22, 4021-4024; (f) K. Mori, Y. B. Seu,  Tetrahedron  1985, 41, 3429-3431; (g) F. Sato, O. Takahashi, T. Kato, Y. Kobayashi,  J. Chem. Soc., Chem. Commun.  1985, 1638-1641; (h) S. Hatakeyama, K. Sakurai, S. Takano, J. Chem. Soc., Chem. Commun. 1985, 1759-1761; (i) A. Yusufoglu, S. Antons, H. D. Scharf,  J. Org. Chem.  1986, 51, 3485-3487; (j) J. Mulzer, A. Angermann, W. Munch,  Liebigs Ann. Chem.  1986, 825-838; (k) H. Redlich, W. Bruns, W. Francke, V. Schurig, T. L. Payne, J. P. Vite,  Tetrahedron  1987, 43, 2029-2034; (l) J. M. Chong, E. K. Mar,  Tetrahedron  1989, 45, 7709-7716; (m) Y. Noda, M. Kikuchi,  Chem. Lett.  1989, 1755-1756; (n) S. Ramaswamy, A. C. Oehlschlager,  J. Org. Chem.  1989, 54, 255-257; (o) K. Matsumoto, N. Suzuki, H. Ohta,  Tetrahedron Lett.  1990, 31, 7163-7166; (p) G. Pedrocchifantoni, S. Servi,  J. Chem. Soc., Perkin  1 1991, 1764-1765; (q) V. Cere, C. Mazzini, C. Paolucci, S. Pollicino, A. Fava,  J. Org. Chem.  1993, 58, 4567-4571; (r) J. A. Soderquist, A. M. Rane,  Tetrahedron Lett.  1993, 34, 5031-5034; (s) A. Gypser, M. Flasche, H. D. Scharf,  Liebigs Ann. Chem.  1994, 775-780; (t) M. J. Kim, G. B. Choi, J. Y. Kim, H. J. Kim,  Tetrahedron Lett.  1995, 36, 6253-6256; (u) S. Vettel, C. Lutz, P. Knochel,  Synlett  1996, 731-733; (v) J. K. Gallos, L. C. Kyradjoglou, T. V. Koftis,  Heterocycles  2001, 55, 781-784; (w) H.-Y. Lee, Y. Jung, H. Moon,  Bull. Korean Chem. Soc.  2009, 30, 771-772). 
         [0083]    (+)-Endo-brevicomin is a male produced component of the attractive pheromone system of  Dendroctonus frontalis  (southern pine beetle), a tree-killing insect found in southern North America and Central America (see R. M. Silverstein, R. G. Brownlee, T. E. Bellas, D. L. Wood, L. E. Browne,  Science  1968, 159, 889-891). It was envisioned that AROCM of 10 with 4-penten-2-ol would set the relative and absolute stereochemistry in the synthesis of (+)-endo brevicomin. 
         [0084]    An expedient three-step synthesis of (+)-endo brevicomin was accomplished featuring the AROCM of 10 with racemic 16 to afford 17 (91% Z) in 85% yield as an inconsequential mixture of diastereomers (Scheme 5). The mixture of epimeric alcohols was cleanly oxidized to the desired ketone by Dess-Martin periodinane in 88% yield. Z-18 was obtained in 95% ee, indicating high enantioselectivity in the AROCM reaction. Hydrogenation of Z-18 in acidic methanol resulted in concomitant reduction of the alkenes, hydrogenolysis of the benzyl groups and cyclization to form (+)-endo brevicomin in 67% yield in a one-pot transformation (The absolute configurations of the AROCM products in this study were assigned by analogy to 19 and 21). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0085]    It was envisioned that the synthetic utility of the 1,5-dienes produced in the AROCM of cyclobutenes could be further underscored by chemoselective functionalization of the two alkenes. For example, the introduction of additional hydroxyl groups would enable the rapid synthesis of monosaccharides. In this fashion, a succinct and highly enantioselective synthesis of biologically relevant monosaccharides could function as a robust route to starting materials for complex polysaccharides. 
         [0086]    The synthesis of ribose derivative 21 was carried out to demonstrate the conversion of AROCM products such as 15 into useful monosaccharides (Scheme 6). Dihydroxylation of Z-15f catalyzed by OsO 4  afforded a 66% yield of differentially protected pentanol 20 in 9:1 dr (see (a) J. K. Cha, W. J. Christ, Y. Kishi,  Tetrahedron Lett.  1983, 24, 3943-3946; (b) W. J. Christ, J. K. Cha, Y. Kishi,  Tetrahedron Lett.  1983, 24, 3947-3950). Ozonolysis of the remaining double bond afforded the differentially protected L-ribose lactol, which was isolated as methyl glycoside 21 in 47% yield over two steps (see (a) R. R. Schmidt, A. Gohl,  Chem. Ber.  1979, 112, 1689-1704; (b) P. A. Wender, F. C. Bi, N. Buschmann, F. Gosselin, C. Kan, J.-M. Kee, H. Ohmura,  Org. Lett.  2006, 8, 5373-5376). It is hypothesized that a broader collection of monosaccharides will be accessible from the AROCM products by the modification of this synthetic sequence. 
         [0000]    
       
                 
         
             
             
         
       
     
       Enatioenriched Catalysts 
       [0087]    It was proposed that in addition to employing a catalyst with the large chelating adamantyl group (e.g. catalyst 4), further steric bulk could be installed by modification of the X-type ligand. In order to better understand how the X-type ligand affected the enantioselectivity, complexes 22a-h were prepared by ligand exchange from iodide 1. This reaction proceeded rapidly and afforded products of sufficient purity after concentration, re-dissolution in benzene, and filtration through a short plug of Celite (Scheme 7). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0088]    Complexes containing achiral carboxylates (22a-c) and enantiopure carboxylates (22d-h) were obtained (Scheme 8). 
         [0000]    
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
     
       Catalyzed Asymmetric Ring Opening/Cross Metathesis of Bicyclic Olefins and α-Olefins 
       [0089]    Two of the novel catalysts depicted in Scheme 8 were employed in ring opening cross metathesis reactions (see Schemes x and x). While the O-methyl mandelate derived catalyst 22e afforded 57% yield of highly Z product, the enantioselectivity was modest (28%) (Scheme 9). The catalyst derived from L-N-acetyl alanine (221) afforded the ring opening cross product with &gt;95% Z-selectivity and in 84% ee (Scheme 10). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    
       
                 
         
             
             
         
       
     
         [0090]    Nitrate 4 catalyzed the AROCM of benzonorbornadiene (23) with allyl acetate (6) in 55% yield, 76% Z-selectivity, while both Z and E isomers had &gt;98% ee (see Scheme 11). AROCM of substrate 25, bearing the 7-syn benzyloxy substituent, afforded 26 as a mixture of isomers favoring the E product (18:85 Z/E ratio) in 94% and 93% ee (Z and E isomers respectively) (see Scheme 12). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    
       
                 
         
             
             
         
       
     
         [0091]    It is to be understood that while the invention has been described in conjunction with specific embodiments thereof, that the description above as well as the examples that follow are intended to illustrate and not limit the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains. 
       EXPERIMENTAL 
     General Information—Materials and Methods 
       [0092]    In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. Unless indicated otherwise, temperature is in degrees C. and pressure is at or near atmospheric. The examples are to be considered as not being limiting of the invention as described herein and are instead provided as representative examples of the catalyst compounds of the invention, the methods that may be used in their preparation, and the methods of using the inventive catalysts. 
         [0093]    All reactions were carried out in dry glassware under an Argon atmosphere using standard Schlenk line techniques or in a Vacuum Atmospheres glovebox under nitrogen atmosphere. All solvents were purified by passage through solvent purification columns and further degassed with Argon (see Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J.,  Organometallics  1996, 15, 1518-1520). NMR solvents for air-sensitive compounds were degassed by sparging with nitrogen and passed through a solvent purification column prior to use. Commercially available reagents were used as received unless otherwise noted. Substrates in the liquid state were degassed with Argon and passed through a plug of neutral alumina prior to use. Solid substrates were used after purification by silica gel column chromatography. Silica gel used for the purification of transition metal complexes was dried at 220° C. and 100 mTorr for 24 h prior to use. 
         [0094]    Standard NMR spectroscopy experiments were conducted on a Varian INOVA 500 ( 1 H: 500 MHz,  13 C: 125 MHz) spectrometer. Chemical shifts are referenced to the residual solvent peak (CDCl 3  or C 6 D 6 ) multiplicity is reported as follows: (s: singlet, d: doublet, t: triplet: q: quartet, br: broad, m: multiplet). Spectra were analyzed and processed using MestReNova. 
         [0095]    Gas chromatography data was obtained using an Agilent 6850 FID gas chromatograph equipped with an Agilent HP-5 5% phenyl methyl siloxane capillary column (J&amp;W Scientific). GC instrument conditions: Inlet temperature—250° C.; Detector temperature—300° C.; Hydrogen flow—30 mL/min; Air flow—400 mL/min; Makeup flow—25 mL/min. GC method: 50° C. for 1 min, then temperature ramp (35° C./min) for 7 min to 300° C. followed by an isothermal period at 300° C. for 3 min. 
         [0096]    Chiral gas chromatography was carried out on an Agilent 6850 FID gas chromatograph equipped with an Agilent GTA column. GC instrument conditions: Inlet temperature—180° C.; Detector temperature—250° C.; Hydrogen flow—32 mL/min; Air flow—400 mL/min; Makeup flow—30 mL/min. GC method: 80° C. for 12 min, isocratic. 
         [0097]    High-resolution mass spectra (HRMS) data was obtained on a JEOL MSRoute mass spectrometer using FAB+, EI+, or MALDI-TOF methods. 
         [0098]    Analytical SFC data was obtained on a Mettler SFC supercritical CO 2  analytical chromatography system equipped with Chiracel OD-H, OJ-H or Chirapak AD-H columns (4.6 mm×25 cm). Column temperature was maintained at 40° C. Preparative HPLC was conducted on an Agilent HPLC system equipped with Chiral Technologies Chiralpak AD-H column (21×250 mm) Optical rotations were measured on a Jasco P-2000 polarimeter using a 100 mm path-length cell at 589 nm. 
       EXAMPLES 
     Example 1 
     Preparation of Silver Carboxylate 2 
       [0099]    (S)-phenylmethoxy acetic acid (0.2 g, 1.2 mmol, 2 equiv.) was added to a stirring suspension of silver oxide (0.14 g, 0.6 mmol, 1 equiv.) in 5 mL deionized water shielded from light. The reaction was vigorously stirred for 3 h, at which time a light gray precipitate had formed. The mixture was filtered and washed with water, methanol, and hexanes. The resultant solid was dried under vacuum overnight while shielded from light to provide 0.264 g (0.971 mmol, 81% yield) of silver carboxylate 2.  1 H NMR (500 MHz, DMSO-d 6 ) δ 7.41-7.36 (m, 2H), 7.30-7.25 (m, 2H), 7.25-7.19 (m, 1H), 4.64 (s, 1H), 3.28 (s, 3H).  13 C NMR (125 MHz, DMSO-d 6 ) δ 173.7, 139.8, 127.7, 127.2, 126.9, 84.9, 56.5. HRMS (MALDI-TOF) calculated for C 9 H 9 O 3  [M−Ag] − : 165.0552. found 165.0553. 
       Example 2 
     Preparation of Complex 3 
       [0100]    Ruthenium iodide 1 (0.150 g, 0.215 mmol) and silver carboxylate 2 (0.117 g, 0.430 mmol, 2 equiv.) were added to a round bottom flask in a glovebox. THF (5 mL) was then added, and the suspension stirred for 1.5 h, at which time the color had changed from dark brown to purple. The mixture was concentrated and redissolved in benzene. The suspension was filtered through Celite and subsequently concentrated to afford a 1:1 mixture of carboxylates, 3 and 3′ (153 mg, 0.209 mmol, 97% yield). Pure carboxylate 3 (70.8 mg, 0.097 mmol, 90% of theoretical yield) was isolated by flash chromatography (2 cm×19 cm, 50% ether/pentane eluent) under an inert atmosphere.  1 H NMR (500 MHz, C 6 D 6 ) δ 14.90 (s, 1H), 7.53-7.48 (m, 2H), 7.39 (dd, J=7.5, 1.7 Hz, 1H), 7.19-7.13 (m, 1H), 7.05-6.99 (m, 2H), 6.97-6.92 (m, 1H), 6.92-6.89 (m, 1H), 6.85-6.79 (m, 2H), 6.54 (d, J=8.4 Hz, 1H), 4.51 (m, 1H), 4.23 (s, 1H), 4.12 (s, 1H), 3.49 (m, 1H), 3.41-3.35 (m, 1H), 3.34 (s, 3H), 3.30-3.24 (m, 1H), 3.19 (m, 1H), 2.45 (s, 3H), 2.43 (s, 3H), 2.42-2.39 (m, 1H), 2.26 (s, 3H), 2.18-2.08 (m, 2H), 2.03 (m, 1H), 2.00-1.93 (m, 1H), 1.83 (m, 1H), 1.64 (br, 1H), 1.59-1.52 (m, 1H), 1.49 (m, 1H), 1.45-1.38 (m, 1H), 1.24 (d, J=6.5 Hz, 3H), 1.17-1.06 (m, 2H), 0.64-0.56 (m, 1H), 0.39 (d, J=6.2 Hz, 3H).  13 C NMR (125 MHz, C 6 D 6 ) δ 258.6, 214.9, 177.3, 154.4, 143.7, 139.2, 138.0, 137.9, 137.0, 136.3, 129.5, 129.5, 128.5, 128.0, 127.4, 125.5, 123.0, 122.9, 113.3, 84.9, 74.4, 69.2, 62.9, 56.5, 51.5, 43.3, 41.5, 40.6, 38.2, 38.0, 37.2, 33.6, 31.1, 29.9, 21.2, 21.2, 19.5, 18.9, 18.8. HRMS (FAB+) calculated for C 41 H 49 O 4 RuN 2  [M−H − ]: 735.2736. found 735.2757. The crystal structure of complex 3 is shown below in  FIG. 2 , (details are included in Tables 6-7). 
         [0000]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 6 
               
               
                   
               
               
                 Crystal data and structural analysis details of 3. 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Type of diffractometer 
                 Bruker APEX-II CCD 
                   
               
               
                 Wavelength 
                 0.71073 Å MoK 
                   
               
               
                 Data collection temperature 
                 100 K 
                   
               
               
                 Empirical formula 
                 C 41 H 50 N 2 O 4 Ru 
                   
               
               
                 Formula weight 
                 735.90 
                   
               
               
                 Crystal system 
                 monoclinic 
                   
               
               
                 Space group 
                 P 1 21 1 (# 4) 
                   
               
               
                 Theta range for  
                 2.76 to 42.71° 
                   
               
               
                 9040 reflections used 
                   
                   
               
               
                 in lattice determination 
                   
                   
               
               
                 Unit cell dimensions 
                 a = 9.6582(6) Å 
                 α = 90° 
               
               
                   
                 b = 14.7827(9) Å 
                 β = 105.749(3)° 
               
               
                   
                 c = 12.9177(8) Å 
                 γ = 90° 
               
               
                 Volume 
                 1775.08(19) Å 3   
                   
               
               
                 Z 
                 2 
                   
               
               
                 Density (calculated) 
                 1.377 g/cm 3   
                   
               
               
                 F(000) 
                 772 
                   
               
               
                 Theta range for data  
                 1.6 to 43.7° 
                   
               
               
                 collection 
                   
                   
               
               
                 Completeness to  
                 99.9% 
                   
               
               
                 theta = 25.000° 
                   
                   
               
               
                 Index ranges 
                 −18 ≦ h ≦ 18, −28 ≦ k ≦ 27,  
                   
               
               
                   
                 −25 ≦ 1 ≦ 25 
                   
               
               
                 Reflections collected 
                 171955 
                   
               
               
                 Independent reflections 
                 26091 [R int  = 0.0459] 
                   
               
               
                 Reflections &gt; 2σ(I) 
                 24002 
                   
               
               
                 Average σ(I)/(net I) 
                 0.0350 
                   
               
               
                 Absorption coefficient 
                 0.49 mm −1   
                   
               
               
                 Absorption correction 
                 Semi-empirical from  
                   
               
               
                   
                 equivalents 
                   
               
               
                 Max. and min. transmission 
                 1.0000 and 0.9117 
                   
               
               
                 Goodness-of-fit on F 2   
                 1.24 
                   
               
               
                 Final R indices [I &gt; 2σ(I), 
                 R1 = 0.0252, wR2 = 0.0534 
                   
               
               
                 24002 reflections] 
                   
                   
               
               
                 R indices (all data) 
                 R1 = 0.0303, wR2 = 0.0547 
                   
               
               
                 Primary solution method 
                 dual 
                   
               
               
                 Hydrogen placement 
                 geom 
                   
               
               
                 Refinement method 
                 Full-matrix least-squares  
                   
               
               
                   
                 on F 2   
                   
               
               
                 Data/restraints/parameters 
                 26091/1/439 
                   
               
               
                 Treatment of hydrogen 
                 constr 
                   
               
               
                 atoms 
                   
                   
               
               
                 Type of weighting scheme  
                 calc 
                   
               
               
                 used 
                   
                   
               
               
                 Weighting scheme used 
                   
                   
               
               
                 Max shift/error 
                 0.001 
                   
               
               
                 Average shift/error 
                 0.000 
                   
               
               
                 Absolute structure parameter 
                 −0.009(4) 
                   
               
               
                 Extinction coefficient 
                 n/a 
                   
               
               
                 Largest diff. peak and hole 
                 1.15 and −0.44 e · Å −3   
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Atomic coordinates (×10 4 ) and equivalent isotropic displacement  
               
               
                 parameters (Å 2  × 10 3 ) for 3. U(eq) is defined as 
               
               
                 one third of the trace of the orthogonalized U ij  tensor. 
               
             
          
           
               
                   
                 x 
                 y 
                 z 
                 U eq   
               
               
                   
               
               
                 Ru(1)   
                 8019(1) 
                 7506(1) 
                 8590(1) 
                  8(1) 
               
               
                 O(1)  
                 7144(1)  
                 6189(1) 
                 7675(1) 
                 12(1) 
               
               
                 O(2)  
                 6468(1)  
                 7617(1)  
                 9731(1) 
                 14(1) 
               
               
                 O(3)  
                 8396(1)  
                 6752(1)  
                 10126(1)  
                 12(1) 
               
               
                 O(4)  
                 5955(1)  
                 7368(1)  
                 11626(1)  
                 19(1) 
               
               
                 N(1)  
                 8574(1) 
                 9390(1) 
                 8447(1)  
                 13(1) 
               
               
                 N(2)  
                 9586(1) 
                 9005(1) 
                 10111(1)  
                 15(1) 
               
               
                 C(1)  
                 8834(1) 
                 8683(1)  
                 9138(1)  
                 11(1) 
               
               
                 C(2)  
                 9015(1) 
                 10264(1)  
                 8967(1) 
                 18(1) 
               
               
                 C(3)  
                 10043(2)  
                 9958(1) 
                 10029(2)  
                 20(1) 
               
               
                 C(4)  
                 7660(1)  
                 9241(1) 
                 7359(1)  
                 11(1) 
               
               
                 C(5)  
                 6838(1) 
                 8362(1) 
                 7423(1) 
                 10(1) 
               
               
                 C(6)  
                 5957(1)  
                 8100(1) 
                 6286(1)  
                 13(1) 
               
               
                 C(7)  
                 6896(1) 
                 8010(1)  
                 5506(1)  
                 16(1) 
               
               
                 C(8)  
                 7659(1) 
                 8911(1)  
                 5443(1)  
                 16(1) 
               
               
                 C(9)  
                 6537(1) 
                 9657(1)  
                 5043(1)  
                 16(1) 
               
               
                 C(10) 
                 5611(1) 
                 9758(1) 
                 5832(1) 
                 15(1) 
               
               
                 C(11) 
                 6569(1) 
                 10012(1)  
                 6956(1) 
                 15(1) 
               
               
                 C(12) 
                 4835(1) 
                 8855(1) 
                 5873(1) 
                 16(1) 
               
               
                 C(13) 
                 8594(1) 
                 9151(1)  
                 6567(1) 
                 15(1) 
               
               
                 C(14) 
                 10092(1)  
                 8526(1) 
                 11100(1)  
                 14(1) 
               
               
                 C(15) 
                 11297(1)  
                 7958(1) 
                 11276(1)  
                 15(1) 
               
               
                 C(16) 
                 11805(1)  
                 7545(1) 
                 12283(1)  
                 18(1) 
               
               
                 C(17) 
                 11158(2)  
                 7690(1) 
                 13107(1)  
                 21(1) 
               
               
                 C(18) 
                 9965(2) 
                 8259(1) 
                 12906(1)  
                 20(1) 
               
               
                 C(19) 
                 9417(1) 
                 8683(1)  
                 11915(1)  
                 17(1) 
               
               
                 C(20) 
                 12040(1)  
                 7778(1) 
                 10415(1)  
                 21(1) 
               
               
                 C(21) 
                 11727(2)  
                 7244(1) 
                 14189(1)  
                 31(1) 
               
               
                 C(22) 
                 8095(2)  
                 9269(1) 
                 11741(1)  
                 25(1) 
               
               
                 C(23) 
                 9469(1)  
                 7226(1)  
                 7959(1)  
                 12(1) 
               
               
                 C(24) 
                 9291(1)  
                 6462(1)  
                 7223(1)  
                 12(1) 
               
               
                 C(25) 
                 10239(1)  
                 6274(1)  
                 6600(1) 
                 17(1) 
               
               
                 C(26) 
                 9944(2)  
                 5597(1)  
                 5824(1)  
                 21(1) 
               
               
                 C(27) 
                 8694(2)  
                 5084(1)  
                 5676(1)  
                 21(1) 
               
               
                 C(28) 
                 7745(1) 
                 5242(1) 
                 6296(1)  
                 16(1) 
               
               
                 C(29) 
                 8034(1) 
                 5930(1)  
                 7054(1) 
                 12(1) 
               
               
                 C(30) 
                 5784(1)  
                 5695(1)  
                 7524(1)  
                 14(1) 
               
               
                 C(31) 
                 6063(1)  
                 4807(1) 
                 8131(1) 
                 22(1) 
               
               
                 C(32) 
                 4742(1) 
                 6293(1) 
                 7899(1)  
                 18(1) 
               
               
                 C(33) 
                 7310(1) 
                 7090(1) 
                 10359(1)  
                 11(1) 
               
               
                 C(34) 
                 7073(1) 
                 6819(1)  
                 11439(1)  
                 13(1) 
               
               
                 C(35) 
                 6738(1) 
                 5820(1) 
                 11442(1)  
                 13(1) 
               
               
                 C(36) 
                 7738(1)  
                 5217(1) 
                 12033(1)  
                 25(1) 
               
               
                 C(37) 
                 7458(2) 
                 4291(1) 
                 11982(2)  
                 34(1) 
               
               
                 C(38) 
                 6163(2) 
                 3965(1) 
                 11337(1)  
                 28(1) 
               
               
                 C(39) 
                 5138(2)  
                 4566(1) 
                 10771(1)  
                 27(1) 
               
               
                 C(40) 
                 5419(1)  
                 5487(1) 
                 10819(1)  
                 22(1) 
               
               
                 C(41) 
                 5945(2)  
                 7337(1)  
                 12722(1)  
                 25(1) 
               
               
                   
               
             
          
         
       
     
       Example 3 
     Preparation of Catalyst 4 
       [0101]    To a solution of ruthenium carboxylate 3 (56.5 mg, 0.0769 mmol) in 5 mL THF was added para-toluenesulfonic acid monohydrate (14.6 mg, 0.0769 mmol, 1 equiv.) to instantly afford a green/blue solution. Sodium nitrate (32.7 mg, 0.384 mmol, 5 equiv.) was added and then methanol was added dropwise until the solution turned purple. The purple solution was allowed to stir for 15 min., at which time it was concentrated. The resultant crude mixture was redissolved in THF, filtered through Celite, and concentrated. Elution through a silica gel plug afforded pure nitrate 4 (21 mg, 0.033 mmol, 43% yield), which was spectroscopically identical to the previously reported complex (see Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H.  J. Am. Chem. Soc.  2012, 134, 693). 
       Substrates for Catalyzed AROCM of Bicyclic Olefins and α-Olefins 
       [0102]    Substrates for AROCM were synthesized as previously reported in the literature: 5 (see Wang, L.; RajanBabu, T. V.  J. Org. Chem.  2010, 75, 7636) and starting materials to generate 9a (see R. Alder  Chem. Ber.  1955, 88, 407-416), 9b (see Takebayashi, S.; John, J. M.; Bergens, S. H.  J. Am. Chem. Soc.  2010, 132, 12832-12834), 9d (see Tiede, S.; Berger, A.; Schlesiger, D.; Rost, D.; Lühl, A.; Blechert, S.  Angew. Chem., Int. Ed.  2010, 49, 3972-3975), 9e (see Van Veldhuizen, J. J.; Garber, S. B.; Kingsbury, J. S.; Hoveyda, A. H.  J. Am. Chem. Soc.  2002, 124, 4954-4955) were synthesized according to the provided references. 
       General Procedure for Catalyzed AROCM of Bicyclic Olefins and α-Olefins 
       [0103]    In a glovebox, norbornene 7 (33 mg, 0.1 mmol, 1 equiv) and allyl acetate (70 mg, 0.7 mmol, 7 equiv) were dissolved in 0.15 mL THF. To this solution was added 50 μL of a stock solution (0.02 M in THF) of catalyst 4. The reaction vial was capped and stirred for 1 h and then quenched with an excess of ethyl vinyl ether. The reaction mixture was concentrated and Z/E ratios were determined by 500 MHz  1 H NMR (products 7, 8a-e) or GC (products 9a-e). The crude was subjected to flash chromatography or preparative TLC to afford the desired AROCM product (7, 27.9 mg, 64% yield, 95:5 Z/E, 93% ee). Pure products were submitted to analytical SFC to determine ee. 
       Example 4 
       [0104]    Characterization data for AROCM product Benzyl ether 7, 64% yield, 95% Z. [α] D   25 +36.6° (c=1.39, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.36-7.27 (m, 10H), 5.85 (ddd, J=17.1, 10.1, 8.3 Hz, 1H), 5.65 (t, J=10.7 Hz, 1H), 5.48 (m, 1H), 4.99 (ddd, J=17.1, 2.1, 1.1 Hz, 1H), 4.92 (ddd, J=10.2, 2.1, 0.8 Hz, 1H), 4.66 (ddd, J=12.7, 7.4, 1.3 Hz, 1H), 4.55 (ddd, J=12.6, 6.4, 1.4 Hz, 1H), 4.38 (dd, J=11.8, 2.3 Hz, 2H), 4.35 (d, J=11.8 Hz, 2H), 3.53-3.37 (m, 4H), 3.16-3.00 (m, 1H), 2.82-2.68 (m, 1H), 2.49-2.37 (m, 2H), 2.03 (s, 3H), 1.98 (dt, J=12.9, 8.2 Hz, 1H), 1.64-1.53 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 171.1, 140.5, 138.6, 138.6, 137.6, 128.4, 128.0, 127.9, 127.6, 123.2, 114.6, 73.4, 73.3, 68.8, 68.6, 60.6, 45.9, 45.8, 45.6, 38.8, 38.7, 21.2. HRMS (EI+) calculated for C 21 H 27 O 3  [M−OBn]: 327.1960. found 327.1966. 
         [0105]    Separation conditions: OD-H, 5% IPA, 2.5 mL/min. 93% ee 

 
       Racemate: 
       [0106]      
         [0000]                                                                            Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1   23.467   BV   9.5111   1044.70398   30.53812   49.8296       2   25.004   VB   0.5167   1051.84814   28.89583   50.1704            Totals:   2096.55212   59.43396                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 23.012 
                 BV 
                 0.3973 
                 451.99329 
                  14.12780 
                 3.3052 
               
               
                 2 
                 24.210 
                 VB 
                 0.6641 
                  1.32231e4 
                 308.47403 
                 96.6948 
               
             
          
           
               
                 Totals: 
                  1.36751e4 
                 322.60183 
                   
               
               
                   
               
             
          
         
       
     
       Example 5 
       [0107]    Characterization data for AROCM product Carbamate 8a, 41% yield, 95% Z. [α] D   25 +25.4° (c=0.50, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.36-7.27 (m, 10H), 5.84 (ddd, J=17.1, 10.2, 8.2 Hz, 1H), 5.51 (t, J=10.5 Hz, 1H), 5.45-5.33 (m, 1H), 4.98 (ddd, J=17.1, 2.1, 1.1 Hz, 1H), 4.92 (ddd, J=10.2, 2.1, 0.8 Hz, 1H), 4.71 (s, 1H), 4.44-4.32 (m, 4H), 3.83-3.64 (m, 2H), 3.52-3.37 (m, 4H), 3.07 (m, 1H), 2.78-2.66 (m, 1H), 2.51-2.33 (m, 2H), 1.97 (dt, J=12.9, 8.2 Hz, 1H), 1.54-1.48 (m, 1H), 1.43 (s, 9H).  13 C NMR (125 MHz, CDCl 3 ) δ 155.9, 140.3, 138.6, 138.5, 135.9, 128.4, 128.4, 128.4, 128.0, 127.9, 127.7, 127.6, 127.6, 125.6, 114.6, 73.3, 73.2, 68.8, 68.6, 46.0, 45.8, 45.8, 38.6, 38.2, 37.6, 28.6. HRMS (EI+) calculated for C 31 H 41 O 4 N [M+]: 491.3036. found 491.3038. 
         [0108]    Separation conditions: OD-H, 10% IPA, 2.5 mL/min. 94% ee 
         [0000]    Racemate: 

 
         [0000]                                                                            Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1   16.314   BB   0.4076   2501.07446    93.63906   51.1753       2   19.228   BBA   0.4768   2386.19580    76.72945   48.8247            Totals:   4887.27026   170.36851                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
               
                 1 
                 16.842 
                 BB 
                 0.3219 
                  126.93304 
                  4.77848 
                  2.7575 
               
               
                 2 
                 19.674 
                 BB 
                 0.4971 
                 4476.19385 
                 141.46957 
                 97.2425 
               
             
          
           
               
                 Totals: 
                 4603.12689 
                 146.24805 
                   
               
               
                   
               
             
          
         
       
     
       Example 6 
       [0109]    Characterization data for AROCM product Ester 8b, 65% yield, 95% Z, ee was determined on derivative S1. [α] D   25 +31.8° (c=1.53, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.35-7.26 (m, 10H), 5.86 (ddd, J=17.1, 10.1, 8.4 Hz, 1H), 5.46-5.37 (m, 1H), 5.35-5.26 (m, 1H), 4.97 (ddd, J=17.1, 2.2, 1.1 Hz, 1H), 4.90 (ddd, J=10.1, 2.2, 0.8 Hz, 1H), 4.44-4.32 (m, 4H), 4.12 (q, J=7.1 Hz, 2H), 3.52-3.38 (m, 4H), 3.12-2.99 (m, 1H), 2.79-2.68 (m, 1H), 2.55-2.24 (m, 6H), 1.96 (dt, J=12.8, 8.2 Hz, 1H), 1.58-1.48 (m, 1H), 1.25 (t, J=7.1 Hz, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 173.3, 140.9, 138.7, 138.7, 133.5, 128.4, 128.4, 128.0, 127.9, 127.6, 127.6, 127.5, 114.3, 73.32, 73.30, 68.9, 68.8, 60.4, 45.8, 45.7, 45.6, 38.8, 38.6, 34.7, 23.1, 14.4. HRMS (EI+) calculated for C 30 H 38 O 4  [M+]: 462.2770. found 462.2758. 
       Example 7 
       [0110]    Characterization data for AROCM product Alcohol S1, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0111]    Ester 8b was treated with excess DIBAL at 23° C. for 2 h to afford 76% yield of alcohol S1 after workup and silica gel chromatography. 
         [0112]    [α] D   25 +31.3° (c=1.05, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.37-7.27 (m, 10H), 5.86 (ddd, J=17.9, 10.0, 8.3 Hz, 1H), 5.46-5.29 (m, 2H), 4.98 (dd, J=17.2, 1.9 Hz, 1H), 4.91 (dd, J=10.1, 2.0 Hz, 1H), 4.48-4.31 (m, 4H), 3.60 (t, J=6.4 Hz, 2H), 3.46 (m, 4H), 3.06 (m, 1H), 2.74 (m, 1H), 2.43 (m, 2H), 2.12 (q, J=7.3 Hz, 2H), 1.97 (dt, J=12.7, 8.2 Hz, 1H), 1.68-1.47 (m, 3H), 1.44 (s, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 140.8, 138.7, 138.6, 132.8, 129.1, 128.4, 128.4, 128.3, 128.0, 127.9, 127.6, 114.3, 73.32, 73.31, 73.28, 69.0, 68.8, 62.6, 45.7, 45.6, 38.8, 38.5, 32.7, 23.8. HRMS (FAB+) calculated for C 28 H 37 O 3  [M+H]: 421.2743. found 421.2746. 
         [0113]    Separation conditions: OD-H, 15% IPA, 2.5 mL/min. 91% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime   Type   Width   Area   Height   Area       #   (min)       (min)   (mAU*s)   (mAU)   %                    1   9.363   BB   0.2835    837.48871   44.92727   49.7025       2   10.229   BB   0.3081    847.51575   41.18006   50.2975            Totals:   1685.00446   86.10733                        
Enantioenriched 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 9.451 
                 BV 
                 0.3229 
                  1.03224e4 
                 491.82324 
                 95.3861 
               
               
                 2 
                 10.493 
                 VB 
                 0.3077 
                 499.30240 
                  21.13039 
                  4.6139 
               
             
          
           
               
                 Totals: 
                  1.08217e4 
                 512.95363 
                   
               
               
                   
               
             
          
         
       
     
       Example 8 
       [0114]    Characterization data for AROCM product Benzyl ether 8c, 51% yield, 95% Z. [α] D   25 +32.9° (c=1.23, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.42-7.22 (m, 10H), 7.08 (d, J=8.2 Hz, 2H), 6.82 (d, J=8.7 Hz, 2H), 5.89 (m, 1H), 5.50 (dd, J=6.5, 2.5 Hz, 2H), 5.00 (d, J=17.5 Hz, 1H), 4.92 (d, J=10.1 Hz, 1H), 4.48-4.33 (m, 4H), 3.78 (s, 3H), 3.60-3.44 (m, 4H), 3.39 (dd, J=15.6, 5.8 Hz, 1H), 3.29 (dd, J=15.6, 5.3 Hz, 1H), 3.17 (m, 1H), 2.77 (m, 1H), 2.58-2.37 (m, 2H), 2.02 (dt, J=12.7, 8.1 Hz, 1H), 1.67-1.55 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 157.9, 140.9, 138.7, 138.69, 133.3, 132.7, 129.3, 128.6, 128.4, 128.4, 128.0, 128.0, 127.9, 127.6, 127.57, 114.3, 113.9, 73.35, 73.33, 69.0, 68.9, 55.4, 45.8, 45.76, 45.74, 45.7, 38.9, 38.7, 32.8. HRMS (FAB+) calculated for C 33 H 39 O 3  [M+H]: 483.2899. found 483.2878. 
         [0115]    Separation conditions: AD-H, 20% IPA, 2.5 mL/min. 81% ee 
         [0000]    Racemate 

 
         [0000]                                                                            Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1   5.678   BV   0.1849   4131.27295   328.10538   49.8705       2   6.289   VB   0.2028   4152.73145   297.64392   50.1295            Totals:   8284.00439   625.74930                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
               
                 1 
                 5.658 
                 VV 
                 0.1862 
                  986.96069 
                  78.75704 
                  9.4299 
               
               
                 2 
                 6.263 
                 VB 
                 0.2132 
                 9479.31836 
                 661.58344 
                 90.5701 
               
             
          
           
               
                 Totals: 
                   1.04663e4 
                 740.34048 
                   
               
               
                   
               
             
          
         
       
     
       Example 9 
       [0116]    Characterization data for AROCM product Boronic ester 8d, 48% yield, 95% Z. [α] D   25 +12.8° (c=0.85, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.35-7.26 (m, 10H), 5.88 (ddd, J=17.1, 10.1, 8.5 Hz, 1H), 5.54-5.43 (m, 1H), 5.41-5.32 (m, 1H), 4.97 (ddd, J=17.1, 2.2, 1.1 Hz, 1H), 4.89 (ddd, J=10.1, 2.2, 0.8 Hz, 1H), 4.39 (dd, J=11.8, 3.9 Hz, 2H), 4.34 (dd, J=11.8, 3.8 Hz, 2H), 3.54-3.41 (m, 4H), 3.02 (m, 1H), 2.81-2.65 (m, 1H), 2.51-2.33 (m, 2H), 1.97 (dt, J=12.9, 8.2 Hz, 1H), 1.76-1.59 (m, 2H), 1.57-1.49 (m, 1H), 1.23 (s, 12H).  13 C NMR (125 MHz, CDCl 3 ) δ 141.2, 138.8, 132.0, 128.4, 127.9, 127.51, 127.50, 124.3, 114.0, 83.3, 73.3, 73.26, 69.1, 69.0, 45.70, 45.68, 45.3, 38.7, 38.6, 24.92, 24.89. HRMS (EI+) calculated for C 32 H 43 O 4 B [M+]: 502.3254. found 502.3252. 
         [0117]    Separation conditions: OD-H, 5% IPA, 2.5 mL/min. 75% ee 
         [0000]    Racemate: 

 
         [0000]                                                                            Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1    21.313   BB   0.4859   1988.34473    61.38202   48.5113       2   223.201   BB   0.5323   2110.38379    58.03347   51.4887            Totals:   4098.72852   119.41549                        
Enantoenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
               
                 1 
                 21.095 
                 BB 
                 0.4365 
                  310.99133 
                  9.53655 
                 12.3902 
               
               
                 2 
                 22.889 
                 BB 
                 0.5353 
                 2198.98804 
                 62.99510 
                 87.6098 
               
             
          
           
               
                 Totals: 
                 2509.97937 
                 72.53165 
                   
               
               
                   
               
             
          
         
       
     
       Example 10 
       [0118]    Characterization data for AROCM product Benzyl ether 8e, 62% yield, 95% Z. [α] D   25 +28.7° (c=1.3, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.35-7.25 (m, 10H), 5.87 (ddd, J=17.1, 10.1, 8.4 Hz, 1H), 5.39-5.28 (m, 2H), 4.97 (ddd, J=17.2, 2.2, 1.1 Hz, 1H), 4.89 (ddd, J=10.2, 2.2, 0.8 Hz, 1H), 4.42-4.34 (m, 4H), 3.55-3.39 (m, 4H), 3.10-2.93 (m, 1H), 2.74 (m, 1H), 2.46 (m, 1H), 2.38 (m, 1H), 2.12-1.84 (m, 2H), 1.52 (m, 1H), 1.35-1.24 (m, 5H), 0.94-0.81 (m, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 141.1, 138.8, 131.9, 130.2, 128.40, 128.38, 128.0, 127.95, 127.94, 127.6, 127.5, 114.1, 73.3, 73.3, 69.1, 68.9, 45.7, 45.6, 38.9, 38.7, 32.2, 27.3, 22.5, 14.2. HRMS (EI+) calculated for C 29 H 38 O 2  [M+]: 418.2872. found 418.2856. 
         [0119]    Separation conditions: OJ-H, 5% IPA, 2.5 mL/min. 89% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   10.200   MM   0.4618   2528.33081   91.24889   51.9762       2   12.974   MM   0.5422   2336.07202   71.80923   48.0238            Totals:   4864.40283   163.05812                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 10.177 
                 VV 
                 0.3707 
                 1.44529e4 
                 588.22974 
                 94.6063 
               
               
                 2 
                 13.210 
                 VV 
                 0.3531 
                 823.99506 
                 30.31367 
                 5.3937 
               
             
          
           
               
                 Totals: 
                 1.52769e4 
                 618.54341 
                   
               
               
                   
               
             
          
         
       
     
       Example 11 
       [0120]    Characterization data for AROCM product Triacetate 9a, 45% yield, 97% Z. [α] D   25 +23.9° (c=0.58, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 5.80 (ddd, J=17.0, 10.3, 8.0 Hz, 1H), 5.62-5.52 (m, 2H), 5.04 (ddd, J=11.9, 1.8, 1.1 Hz, 1H), 5.02 (ddd, J=5.1, 1.8, 1.1 Hz, 1H), 4.71-4.65 (m, 1H), 4.60-4.55 (m, 1H), 4.14-3.97 (m, 4H), 3.15 (m, 1H), 2.87-2.76 (m, 1H), 2.51 (m, 2H), 2.12 (dt, J=13.4, 8.3 Hz, 1H), 2.06 (s, 3H), 2.03 (s, 3H), 2.03 (s, 3H), 1.49 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 171.1, 170.97, 170.94, 138.8, 136.0, 124.8, 115.9, 62.8, 62.7, 60.3, 45.2, 44.6, 44.3, 38.2, 37.7, 21.2, 21.1. 
         [0121]    HRMS (EI) calculated for C 18 H 26 O 6  [M+]: 338.1729. found 338.1737. 
         [0122]    Separation conditions: OD-H, 3% IPA, 2.5 mL/min. 82% ee 
         [0000]    Racemate: 

 
         [0000]                                                                            Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1   6.037   BB   0.1736   201.35269   18.13161   45.1499       2   7.186   BB   0.1999   244.61229   19.04047   54.8501            Totals:   445.96498   37.17208                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 6.110 
                 BB 
                 0.1233 
                 39.40160 
                 4.28349 
                 9.1737 
               
               
                 2 
                 7.154 
                 BB 
                 0.1978 
                 390.10281 
                 29.59711 
                 90.8263 
               
             
          
           
               
                 Totals: 
                 429.50441 
                 33.88060 
                   
               
               
                   
               
             
          
         
       
     
       Example 12 
       [0123]    Characterization data for AROCM product Imide 9b. The standard conditions were modified to employ 3 mol % of 4 for 5 h. 63% yield, 94% Z. [α] D   25 +14.4° (c=0.28, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.48-7.43 (m, 2H), 7.40-7.35 (m, 1H), 7.26-7.23 (m, 2H), 6.06 (ddd, J=17.4, 10.0, 7.3 Hz, 1H), 5.83-5.76 (m, 1H), 5.76-5.69 (m, 1H), 5.17 (m, 1H), 5.15-5.13 (m, 1H), 4.74-4.70 (m, 1H), 4.70-4.66 (m, 1H), 3.46-3.30 (m, 3H), 3.12-3.01 (m, 1H), 2.07 (s, 3H), 2.04-1.97 (m, 1H), 1.48 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 175.6, 175.5, 141.1, 136.1, 132.7, 131.9, 129.2, 128.7, 126.5, 116.3, 60.1, 49.3, 48.9, 46.6, 40.4, 37.3, 21.2. HRMS (EI) calculated for C 20 H 21 O 4 N [M+]: 339.1471. found 339.1473. 
         [0124]    Separation conditions: AD-H, 10% IPA, 2.5 mL/min. 60% ee 
         [0000]    Racemate: 

 
         [0000]                                                                            Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1   11.263   BB   0.4040   1182.51379   44.22358   50.6270       2   12.608   BB   0.4544   1153.22241   38.40098   49.3730            Totals:   2335.73621   82.62455                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 11.366 
                 BV 
                 0.3278 
                 2275.38013 
                 99.12678 
                 79.8303 
               
               
                 2 
                 12.792 
                 BB 
                 0.3554 
                 574.89026 
                 22.54995 
                 20.1697 
               
               
                   
               
             
          
         
       
     
       Example 13 
       [0125]    Characterization data for AROCM product Anhydride 9c, 58% yield, 98% Z. The ee of anhydride 9c produced by chiral catalyst 4 was measured on derivative S2. [α] D   25 +1.74° (c=0.73, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 5.93 (ddd, J=17.0, 10.4, 7.4 Hz, 1H), 5.76 (ddd, J=10.9, 7.1, 1H), 5.67 (ddd, J=11.1, 9.9, 1H), 5.20 (ddd, J=6.3, 1.3 Hz, 1H), 5.17 (ddd, J=12.8, 1.3 Hz, 1H), 4.68 (ddd, J=12.8, 6.9, 1.3 Hz, 1H), 4.63 (ddd, J=12.8, 7.2, 1.2 Hz, 1H), 3.55-3.46 (m, 2H), 3.42-3.33 (m, 1H), 3.11-2.97 (m, 1H), 2.06 (s, 3H), 2.06-2.00 (m, 1H), 1.41 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 171.0, 170.6, 170.5, 134.7, 131.4, 126.7, 117.6, 59.8, 49.69, 49.68, 49.51, 49.50, 47.0, 40.7, 37.6, 21.1. HRMS (EI) calculated for C 14 H 16 O 5  [M+]: 264.0998. found 264.0989. 
       Example 14 
       [0126]    Characterization data for AROCM product Imide S2. Anhydride 9c was treated with p-bromo aniline (xylenes, reflux, 20 h, 60% yield) to afford the imide S2. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0127]    [α] D   25 +12.5° (c=0.28, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.63-7.53 (m, 2H), 7.19-7.09 (m, 2H), 6.12-5.96 (m, 1H), 5.79-5.68 (m, 2H), 5.17 (m, 1H), 5.14 (ddd, J=5.9, 1.4 Hz, 1H), 4.73-4.69 (m, 1H), 4.69 (m, 1H), 3.47-3.29 (m, 3H), 3.13-3.00 (m, 1H), 2.07 (s, 3H), 2.05-1.96 (m, 1H), 1.50-1.37 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 175.3, 175.1, 171.0, 135.9, 132.5, 132.4, 130.9, 128.0, 125.8, 122.5, 116.4, 60.1, 49.3, 48.9, 46.5, 40.4, 37.2, 21.2. HRMS (FAB+) calculated for C 20 H 21 O 4 N 81 Br [M+H]: 420.0633. found 420.0624. 
         [0128]    Separation conditions: AD-H, 10% IPA, 2.5 mL/min, 75% ee 
         [0000]    Racemate: 

 
         [0000]                                                                            Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1   20.134   VV   0.6044   1900.42920   38.59682   48.6923       2   21.922   CB   0.5698   2002.50818   42.03310   51.3077            Totals:   3902.93738   80.62992                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 20.018 
                 BB 
                 0.4571 
                 208.39857 
                 5.43821 
                 12.4835 
               
               
                 2 
                 21.777 
                 BB 
                 0.4991 
                 1460.98792 
                 36.02553 
                 87.5165 
               
             
          
           
               
                 Totals: 
                 1669.38649 
                 41.46374 
                   
               
               
                   
               
             
          
         
       
     
       Example 15 
       [0129]    Characterization data for AROCM product Imide ent-S3. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0130]    In order to determine the absolute configuration of AROCM products, imides S2 (major product) and ent-S2 (minor product) were separated by preparative chiral HPLC to afford pure samples (&gt;99% e.e.) of each enantiomer. The acetate of imide ent-S2 was removed and the resultant alcohol was acylated with p-nitro benzoyl chloride to give imide ent-S3. [α] D   25 -34° (c=0.09, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.33-8.27 (m, 2H), 8.25-8.18 (m, 2H), 7.61-7.55 (m, 2H), 7.19-7.13 (m, 2H), 6.14-5.97 (m, 1H), 5.90-5.82 (m, 2H), 5.19 (m, 1H), 5.16 (m, 1H), 5.02-4.99 (m, 2H), 3.44 (m, 3H), 3.09 (m, 1H), 2.11-2.00 (m, 2H), 1.50 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 175.2, 175.1, 175.0, 135.85, 135.83, 133.5, 132.4, 130.9, 128.9, 128.8, 128.0, 125.1, 123.7, 122.6, 116.5, 61.4, 49.4, 48.9, 46.6, 40.5, 37.3. The crystal structure of ent-S3 is shown below in  FIG. 3 , (details are included in Tables 8-9). 
         [0000]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 8 
               
               
                   
               
               
                 Crystal Data and Structure Analysis Details for ent-S3. 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Type of diffractometer 
                 Bruker APEX-II CCD 
                   
               
               
                 Wavelength 
                 0.71073 Å MoK 
                   
               
               
                 Data collection temperature 
                 100 K 
                   
               
               
                 Empirical formula 
                 C 25 H 21 BrN 2 O 6   
                   
               
               
                 Formula weight 
                 525.35 
                   
               
               
                 Crystal system 
                 orthorhombic 
                   
               
               
                 Space group 
                 P 21 21 21 (# 19) 
                   
               
               
                 Theta range for 7125 reflections 
                 2.58 to 24.81° 
                   
               
               
                 used in lattice determination 
                   
                   
               
               
                 Unit cell dimensions 
                 a = 6.8772(3) Å 
                 α = 90° 
               
               
                   
                 b = 15.7930(10) Å 
                 β = 90° 
               
               
                   
                 c = 20.9413(12) Å 
                 γ = 90° 
               
               
                 Volume 
                 2274.5(2) Å 3   
                   
               
               
                 Z 
                 4 
                   
               
               
                 Density (calculated) 
                 1.534 g/cm3 
                   
               
               
                 F(000) 
                 1072 
                   
               
               
                 Theta range for data collection 
                 1.9 to 29.8° 
                   
               
               
                 Completeness to theta = 25.000° 
                 99.9% 
                   
               
               
                 Index ranges 
                 −9 ≦ h ≦ 9, −20 ≦ k ≦ 21,  
                   
               
               
                   
                 −27 ≦ 1 ≦ 28 
                   
               
               
                 Reflections collected 
                 34241 
                   
               
               
                 Independent reflections 
                 5864 [R int  = 0.0777] 
                   
               
               
                 Reflections &gt; 2σ(I) 
                 4359 
                   
               
               
                 Average σ(I)/(net I) 
                 0.0925 
                   
               
               
                 Absorption coefficient 
                 1.85 mm-1 
                   
               
               
                 Absorption correction 
                 Semi-empirical from  
                   
               
               
                   
                 equivalents 
                   
               
               
                 Max. and min. transmission 
                 1.0000 and 0.8351 
                   
               
               
                 Goodness-of-fit on F2 
                 1.04 
                   
               
               
                 Final R indices [I &gt; 2σ(I), 4359 
                 R1 = 0.0434,  
                   
               
               
                 reflections] 
                 wR2 = 0.0558 
                   
               
               
                 R indices (all data) 
                 R1 = 0.0789,  
                   
               
               
                   
                 wR2 = 0.0614 
                   
               
               
                 Primary solution method 
                 dual 
                   
               
               
                 Hydrogen placement 
                 geom 
                   
               
               
                 Refinement method 
                 Full-matrix least-squares  
                   
               
               
                   
                 on F2 
                   
               
               
                 Data/restraints/parameters 
                 5864/0/307 
                   
               
               
                 Treatment of hydrogen atoms 
                 constr 
                   
               
               
                 Type of weighting scheme used 
                 calc 
                   
               
               
                 Weighting scheme used 
                   
                   
               
               
                 Max shift/error 
                 0.000 
                   
               
               
                 Average shift/error 
                 0.000 
                   
               
               
                 Absolute structure parameter 
                 0.003(5) 
                   
               
               
                 Extinction coefficient 
                 n/a 
                   
               
               
                 Largest diff. peak and hole 
                 0.67 and −0.47 e · Å-3 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 9 
               
             
             
               
                   
               
               
                 Atomic coordinates (×10 4 ) and equivalent isotropic  
               
               
                 displacement parameters (Å 2  × 10 3 ) for ent-S3. U(eq) is  
               
               
                 defined as one third of the trace of the orthogonalized U ij  tensor. 
               
             
          
           
               
                   
                 x 
                 y 
                 z 
                 Ueq 
               
               
                   
               
               
                 Br(1)  
                  5721(1) 
                 4492(1) 
                 −1710(1)  
                 27(1) 
               
               
                 O(1) 
                  7832(3) 
                 7442(2) 
                  500(1) 
                 17(1) 
               
               
                 O(2) 
                 13037(3) 
                 5688(2) 
                  266(1) 
                 19(1) 
               
               
                 O(3) 
                  8803(3) 
                 8294(2) 
                 3469(1) 
                 25(1) 
               
               
                 O(4) 
                  9757(3) 
                 9519(2) 
                 3918(1) 
                 26(1) 
               
               
                 O(5) 
                  8568(4) 
                 7556(2) 
                 6851(1) 
                 38(1) 
               
               
                 O(6) 
                  9132(5) 
                 6354(2) 
                 6395(1) 
                 47(1) 
               
               
                 N(1) 
                 10188(3) 
                 6447(2) 
                  308(1) 
                 10(1) 
               
               
                 N(2) 
                  8876(4) 
                 7120(2) 
                 6378(2) 
                 25(1) 
               
               
                 C(1) 
                  9451(5) 
                 7168(2) 
                  596(2) 
                 13(1) 
               
               
                 C(2) 
                 10992(5) 
                 7535(2) 
                 1028(2) 
                 12(1) 
               
               
                 C(3) 
                 10491(5) 
                 7511(2) 
                 1751(2) 
                 15(1) 
               
               
                 C(4) 
                 11203(4) 
                 6635(2) 
                 1955(2) 
                 16(1) 
               
               
                 C(5) 
                 13191(4) 
                 6577(2) 
                 1631(2) 
                 15(1) 
               
               
                 C(6) 
                 12773(4) 
                 6936(2) 
                  953(2) 
                 12(1) 
               
               
                 C(7) 
                 12122(5) 
                 6280(2) 
                  478(2) 
                 14(1) 
               
               
                 C(8) 
                  9172(5) 
                 5975(2) 
                 −170(1)  
                 10(1) 
               
               
                 C(9) 
                  9911(4)  
                 5922(2) 
                 −784(2)  
                 12(1) 
               
               
                  C(10) 
                  8912(4)  
                 5470(2) 
                 −1245(2)  
                 16(1) 
               
               
                  C(11) 
                  7170(5)  
                 5089(2) 
                 −1084(2)  
                 14(1) 
               
               
                  C(12) 
                  6416(5)  
                 5143(2) 
                 −474(2)  
                 14(1) 
               
               
                  C(13) 
                  7435(4) 
                 5587(2) 
                  −11(1) 
                 11(1) 
               
               
                  C(14) 
                  8404(5) 
                 7685(3) 
                 1925(2) 
                 20(1) 
               
               
                  C(15) 
                  7773(5) 
                 8174(3) 
                 2392(2) 
                 24(1) 
               
               
                  C(16) 
                  8962(6) 
                 8693(2) 
                 2838(2) 
                 26(1) 
               
               
                  C(17) 
                  9259(6) 
                 8795(2) 
                 3967(2) 
                 18(1) 
               
               
                  C(18) 
                  9085(5) 
                 8327(2) 
                 4588(2) 
                 16(1) 
               
               
                  C(19) 
                  9040(5) 
                 8808(2) 
                 5143(2)  
                 17(1) 
               
               
                  C(20) 
                  8959(5) 
                 8416(2) 
                 5733(2)  
                 18(1) 
               
               
                  C(21) 
                  8944(5) 
                 7548(2) 
                 5749(2)  
                 17(1) 
               
               
                  C(22) 
                  8985(5) 
                 7049(2) 
                 5209(2) 
                 21(1) 
               
               
                  C(23) 
                  9046(5) 
                 7449(2) 
                 4620(2)  
                 18(1) 
               
               
                  C(24) 
                 14163(5) 
                 5731(2) 
                 1661(2)  
                 20(1) 
               
               
                  C(25) 
                 15742(6) 
                 5574(3) 
                 1992(2)  
                 34(1) 
               
               
                   
               
             
          
         
       
     
       Example 16 
       [0131]    Characterization data for AROCM product Anhydride 9d, 65% yield, 96% Z. [α] D   25 +1.96° (c=0.57, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 5.89-5.76 (m, 2H), 5.64 (t, J=10.8 Hz, 1H), 5.20 (d, J=10.2 Hz, 1H), 5.16 (d, J=16.9 Hz, 1H), 4.70 (dd, J=12.7, 7.6 Hz, 1H), 4.59 (dd, J=12.7, 6.6 Hz, 1H), 2.96-2.83 (m, 1H), 2.52 (m, 1H), 2.07 (s, 3H), 1.94 (m, 1H), 1.40 (m, 1H), 1.33 (s, 3H), 1.28 (s, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 173.9, 173.7, 171.0, 134.6, 131.4, 127.3, 118.3, 59.8, 57.8, 57.2, 55.3, 48.2, 37.0, 21.1, 18.3, 18.3. HRMS (FAB+) calculated for C 16 H 21 O 5  [M+H]: 293.1389. found 293.1394. 
         [0132]    Separation conditions: AD-H, 3% IPA, 2.5 mL/min, 95% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   4.099   BV   0.2706   727.27740   33.32114   49.5823       2   4.736   VB   0.2826   739.53021   32.60941   50.4177            Totals:   1466.80762   65.93055                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 4.135 
                 BB 
                 0.2324 
                 20.50533 
                 1.26954 
                 2.4090 
               
               
                 2 
                 4.727 
                 VB 
                 0.2981 
                 830.67578 
                 38.13840 
                 97.5910 
               
             
          
           
               
                 Totals: 
                 851.18111 
                 39.40794 
                   
               
               
                   
               
             
          
         
       
     
       Example 17 
       [0133]    Characterization data for AROCM product Aryl ether 9e. Isolated as a 7:3 mixture of Z/E olefin isomers, 40% yield.  1 H NMR (500 MHz, CDCl 3 ) δ 7.49 (m, 2H), 6.96-6.89 (m, 3H), 5.84 (ddd, J=17.1, 10.3, 7.8 Hz, 2H), 5.82-5.74 (m, 1H), 5.68-5.59 (m, 1H), 5.59-5.51 (m, 1H), 5.09 (m, 1H), 5.04 (m, 1H), 4.69 (m, 1H), 4.52-4.44 (m, 2H), 4.29 (m, 1H), 4.25 (m, 1H), 3.09 (m, 1H), 2.78 (m, 2H), 2.05 (m, 1H), 2.04 (s, 3H), 1.99 (s, 3H), 1.73-1.60 (m, 2H), 1.61-1.50 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 171.0, 170.9, 161.2, 139.5, 139.4, 136.7, 136.3, 126.8, 125.0, 116.2, 116.1, 115.7, 115.6, 89.2, 88.7, 64.9, 60.5, 49.9, 49.9, 49.0, 44.7, 30.2, 29.3, 29.2, 29.16, 21.12, 21.0. HRMS (EI+) calculated for C 19 H 21 O 3 F 3  [M+]: 354.1443. found 354.1429. 
       Examples 18-19 
       [0134]    Characterization data for AROCM product Aryl ether S4. The acetate of aryl ether 9e was removed and the resultant alcohol was acylated with p-nitro benzoyl chloride to afford S4 and S5, which were separable by pTLC. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0135]    [α] D   25 -61.96° (c=0.23, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.30-8.21 (m, 2H), 8.14-8.05 (m, 2H), 7.43 (d, J=8.2 Hz, 2H), 6.91 (d, J=8.8 Hz, 2H), 5.85 (ddd, J=17.1, 10.3, 7.8 Hz, 1H), 5.78-5.66 (m, 2H), 5.10 (ddd, J=17.2, 1.4 Hz, 1H), 5.05 (dd, J=10.3, 1.3 Hz, 1H), 4.98 (dd, J=12.7, 6.4 Hz, 1H), 4.80 (dd, J=12.6, 5.4 Hz, 1H), 4.28 (t, J=5.9 Hz, 1H), 3.19 (m, 1H), 2.86-2.76 (m, 1H), 2.17-2.00 (m, 2H), 1.75-1.64 (m, 1H), 1.64-1.57 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 164.6, 139.2, 137.5, 135.6, 130.8, 126.8, 124.3, 123.6, 116.0, 115.9, 89.2, 61.8, 49.9, 44.8, 30.1, 29.1. HRMS (EI+) calculated for C 24 H 22 O 5 NF 3  [M+]: 461.1450. found 461.1449. 
         [0136]    Separation conditions: OJ-H, 4% IPA, 3.5 mL/min, 95% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   5.863   BV   0.1692   2310.27148   202.36076   49.8647       2   6.896   VV   0.2010   2322.81299   172.60132   50.1353            Totals:   4633.08447   374.96208                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 5.889 
                 VV B 
                 0.1327 
                 118.78459 
                 13.23087 
                 2.4089 
               
               
                 2 
                 6.838 
                 VV 
                 0.1879 
                 4812.26074 
                 379.55093 
                 97.5911 
               
             
          
           
               
                 Totals: 
                 4931.04533 
                 392.78181 
                   
               
               
                   
               
             
          
         
       
     
         [0137]      Characterization data for AROCM product Aryl ether S5. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0138]    [α] D   25 +13.44° (c=0.12, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.31-8.26 (m, 2H), 8.20-8.15 (m, 2H), 7.46 (d, J=8.3 Hz, 1H), 6.93 (d, J=8.2 Hz, 2H), 5.91 (dd, J=15.4, 8.0 Hz, 1H), 5.85 (ddd, J=17.2, 10.3, 7.8 Hz, 1H), 5.75 (ddd, J=15.4, 6.4 Hz, 1H), 5.09 (dd, J=17.2, 1.4 Hz, 1H), 5.08-5.01 (m, 1H), 4.81 (br, 1H), 4.79 (br, 1H), 4.31 (t, J=5.6 Hz, 1H), 2.82 (m, 2H), 2.05 (m, 2H), 1.72-1.61 (m, 2H).  13 C NMR (125 MHz, CDCl 3 ) δ 164.5, 139.4, 138.0, 130.8, 126.8, 124.4, 123.7, 116.2, 115.7, 88.6, 66.3, 49.8, 49.1, 29.2, 29.1. HRMS (EI+) calculated for C 24 H 22 O 5 NF 3  [M+]: 461.1450. found 461.1460. 
         [0139]    Separation conditions: OJ-H, 4% IPA, 3.5 mL/min, 95% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   6.073   FM   0.2053   2256.75928   183.23097   51.8365       2   6.550   MF   0.2055   2096.85425   170.07474   48.1635            Totals:   4353.61353   353.30571                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 6.141 
                 VV 
                 0.1522 
                 131.70372 
                 13.22259 
                 2.6541 
               
               
                 2 
                 6.545 
                 VBA 
                 0.1761 
                 4830.48975 
                 414.04193 
                 97.3459 
               
             
          
           
               
                 Totals: 
                 4962.19347 
                 427.26452 
                   
               
               
                   
               
             
          
         
       
     
       Substrates for Catalyzed AROCM of Monocyclic Olefins and α-Olefins 
       [0140]    Substrates for AROCM were synthesized as previously reported in the literature: substrate 10 (see W. Kirmse, F. Scheidt, H-J. Vater,  J. Am. Chem. Soc.,  1978, 100, 3945), substrate 13a (see A. H. Hoveyda, P. J. Lombardi, R. V. O&#39;Brien, A. R. Zhugralin,  J. Am. Chem. Soc.  2009, 131, 8378), substrate 13b (see (a) T. Mukaiyama, N. Iwasawa,  Chem. Lett.  1984, 753-756; (b) D. A. Evans, J. R. Gage, J. L. Leighton, A. S. Kim,  J. Org. Chem.  1992, 57, 1961-1963; (c) W. Notz, B. List,  J. Am. Chem. Soc.  2000, 122, 7386-7387; (d) M. T. Crimmins, P. J. McDougall,  Org. Lett.  2003, 5, 591-594; (e) A. B. Northrup, D. W. C. MacMillan,  Science  2004, 305, 1752-1755; (f) A. B. Northrup, I. K. Mangion, F. Hettche, D. W. C. MacMillan,  Angew. Chem.  2004, 116, 2204-2206 ; Angew. Chem., Int. Ed.  2004, 43, 2152-2154; (g) S. E. Denmark, W.-J. Chung,  Angew. Chem.  2008, 120, 1916-1918 ; Angew. Chem., Int. Ed.  2008, 47, 1890-1892), substrate 13c (see R. Gandolfi, M. Ratti, L. Toma, C. De Micheli,  Heterocycles  1979, 12, 897), substrate 13d (see A. H. Hoveyda, R. Khan, M. Kashif, P. J. Lombardi, R. V. O&#39;Brien, S. Torker, A. R. Zhugralin,  J. Am. Chem. Soc.  2012, 134, 12438) were synthesized according to the provided references. Catalyst 4 was synthesized as previously reported (see J. Hartung, R. H. Grubbs,  J. Am. Chem. Soc.  2013, 135, 10183). 
       Representative Procedure for Catalyzed AROCM of Monocyclic Olefins and α-Olefins 
       [0141]    In a glovebox, cyclobutene 10 (26.6 mg, 0.1 mmol, 1 equiv) and allyl benzoate (14b, 113 mg, 0.7 mmol, 7 equiv) were dissolved in 0.15 mL THF. To this solution was added 50 μL of a stock solution (0.02 M in THF) of catalyst 4. The reaction vial was capped and stirred for 1.5 h and then quenched with an excess of ethyl vinyl ether. The reaction mixture was concentrated and Z/E ratios were determined by 500 MHz  1 H NMR (products 15a-c, 15e-k) or GC (product 12). The crude was subjected to flash chromatography or preparative TLC to afford the desired AROCM product (15f, 25.9 mg, 61% isolated yield, 88:12 Z/E, 97% ee (Z), 88% ee (E)). Pure products (or E/Z mixtures in the case of 15i, and E-15j) were submitted to analytical SFC to determine enantiomer excess. 
       Example 20 
       [0142]    Characterization data for AROCM product Acetate 12, 79% yield (GC), 85% Z. Z-12. [α] D   25 -9.34° (c=0.52, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.37-7.24 (m, 10H), 5.88-5.77 (2×m, 1H), 5.71-5.64 (m, 1H), 5.34 (m, 1H), 5.29 (m, 1H), 4.64 (AB d, J=10.5 Hz, 1H), 4.63 (AB d, J=10.5 Hz, 1H), 4.61 (m, 1H), 4.51-4.46 (m, 1H), 4.45 (AB d, J=10.5 Hz, 1H), 4.43 (AB d, J=10.5 Hz, 1H), 4.21 (ddd, J=9.1, 5.0, 1.0 Hz, 1H), 3.87 (dd, J=7.5, 5.0 Hz, 1H), 2.04 (s, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 170.8, 138.6, 138.4, 135.5, 131.9, 128.5, 128.4, 128.4, 127.8, 127.7, 127.7, 127.5, 119.2, 82.2, 76.6, 70.7, 70.6, 60.8, 21.1. HRMS (FAB+) calculated for C 23 H 27 O 4  [M+H]: 367.1909. found 367.1904. 
         [0143]    Separation conditions for Z-12: OJ-H, 5% IPA, 2.5 mL/min. 95% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   7.607   VV   0.4141   5907.10059   216.66869   49.4689       2   10.124   VB   0.5585   6033.94629   160.53769   50.5311            Totals:   1.19410e4   377.20638                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 7.955 
                 BV 
                 0.2626 
                  264.61841 
                 14.94419 
                 2.6277 
               
               
                 2 
                 10.319 
                 BV 
                 0.3029 
                 9805.57031 
                 456.01086 
                 97.3723 
               
             
          
           
               
                 Totals: 
                 1.00702e4 
                 470.95505 
                   
               
               
                   
               
             
          
         
       
     
         [0144]    E-12. [α] D   25 -11.8° (c=0.24, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.36-7.24 (m, 10H), 5.88-5.74 (3×m, 1H), 5.33 (m, 1H), 5.29 (m, 1H), 4.65 (AB d, J=9.3 Hz, 1H), 4.63 (AB d, 9.3 Hz, 1H), 4.61 (d, J=6.0 Hz, 2H), 4.45 (AB d, J=10.6 Hz, 1H), 4.43 (AB d, J=10.7 Hz, 1H), 3.89 (dd, J=6.4, 5.1 Hz, 1H), 3.85 (dd, J=7.2, 5.1 Hz, 1H), 2.08 (s, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 170.9, 138.41, 138.33, 135.5, 131.7, 128.46, 128.45, 128.40, 127.8, 127.75, 127.6, 127.55, 119.1, 82.4, 81.3, 70.9, 70.6, 64.4, 21.1. HRMS (FAB+) calculated for C 23 H 27 O 4  [M+H]: 367.1909. found 367.1922. 
         [0145]    Separation conditions for E-12: OJ-H, 7% IPA, 2.5 mL/min. 85% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   7.778   VV   0.2344   2366.55688   148.09634   50.1123       2   8.429   VB   0.2563   2355.94971   137.19626   49.8877            Totals:   4722.50659   285.29260                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 7.842 
                 BV 
                 0.2188 
                 764.89539 
                 48.82001 
                 7.2443 
               
               
                 2 
                 8.336 
                 VB 
                 0.2556 
                 9793.63672 
                 540.08466 
                 92.7557 
               
             
          
           
               
                 Totals: 
                 1.05585e4 
                 588.90466 
                   
               
               
                   
               
             
          
         
       
     
       Example 21 
       [0146]    Characterization data for AROCM product Silyl ether 15a, 66% isolated yield, 88% Z (see S. Saito, H. Itoh, Y. Ono, K. Nishioka, T. Moriwake,  Tetrahedron: Asymmetry  1993, 4, 5). Z-15a: [α] D   25 +4.72° (c=1.06, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 5.84 (ddd, J=17.3, 10.4, 6.4 Hz, 1H), 5.80-5.75 (m, 1H), 5.49 (dddd, J=11.2, 8.9, 1.7, 1.1 Hz, 1H), 5.23 (ddd, J=17.3, 1.8, 1.2 Hz, 1H), 5.16 (ddd, J=10.4, 1.8, 1.0 Hz, 1H), 4.34 (ddd, J=8.9, 7.0, 1.1 Hz, 1H), 4.15 (m, 2H), 3.90 (ddt, J=7.3, 6.4, 1.1 Hz, 1H), 2.31 (br, 1H), 0.88 (s, 9H), 0.86 (s, 9H), 0.05 (s, 3H), 0.03 (s, 3H), 0.02 (s, 3H), 0.01 (s, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 139.3, 134.4, 130.3, 116.5, 77.5, 72.8, 59.3, 26.1, 25.9, 18.5, 18.3, −4.2, −4.2, −4.3, −4.5. HRMS (EI+) calculated for C 19 H 41 O 3 Si 2  [M+H]: 375.2594. found 375.2583. 
         [0147]    Z-15a was derivatized by benzoylation and subsequent desilylation to afford a product spectroscopically identical to Z-15b prior to chiral SFC analysis, which indicated 99% ee (see directly below for racemic trace). 
         [0000]    Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 3.799 
                 BB 
                 0.1373 
                 1.01426e4 
                 1167.74316 
                 99.7523 
               
               
                 2 
                 4.960 
                 BV 
                 0.1919 
                 25.18901 
                 1.83767 
                 0.2477 
               
             
          
           
               
                 Totals: 
                 1.01678e4 
                 1169.58084 
                   
               
               
                   
               
             
          
         
       
     
       Example 22 
       [0148]    Characterization data for AROCM product Diol 15b, 67% isolated yield, 75% Z. Z-15b: [α] D   25 -30.7° (c=0.60, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.06-8.01 (m, 2H), 7.60-7.54 (m, 1H), 7.47-7.41 (m, 2H), 5.89 (ddd, 17.3, 10.5, 6.2 Hz, 1H), 5.93-5.76 (2×m, 1H), 5.38 (ddd, J=17.3, 1.5, 1.4 Hz, 1H), 5.28 (ddd, J=10.6, 1.5, 1.4 Hz, 1H), 5.08 (ddd, J=12.9, 7.7, 0.8 Hz, 1H), 4.83 (ddd, J=12.6, 5.5, 1.0 Hz, 1H), 4.63 (dd, J=8.0, 4.3 Hz, 1H), 4.25 (ddt, J=6.8, 4.3, 1.3 Hz, 1H), 2.85 (br, 1H), 2.34 (br, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 166.9, 136.0, 133.3, 132.5, 130.0, 129.8, 128.6, 127.7, 118.0, 75.5, 70.4, 61.3. HRMS (EI+) calculated for C 14 H 17 O 4  [M+H]: 249.1127. found 249.1117. 
         [0149]    Separation conditions for Z-15b: OD-H, 20% IPA, 2.5 mL/min. 91% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   3.777   BB   0.1325   2620.65259   304.35648   50.0092       2   4.670   BB   0.2558   2619.68433   144.28246   49.9908            Totals:   5240.33691   448.63893                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 3.819 
                 BB 
                 0.1414 
                 4247.60645 
                 453.13589 
                 95.4697 
               
               
                 2 
                 4.999 
                 BB 
                 0.2382 
                  201.56192 
                 13.19609 
                 4.5303 
               
             
          
           
               
                 Totals: 
                 4449.16837 
                 466.33198 
                   
               
               
                   
               
             
          
         
       
     
         [0150]    Characterization data for AROCM product E-15b. [α] D   25 -1.57° (c=0.06, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.08-8.01 (m, 2H), 7.60-7.54 (m, 1H), 7.48-7.41 (m, 2H), 6.02 (dtd, J=15.7, 5.7, 1.3 Hz, 1H), 5.96-5.77 (m, 2H), 5.37 (ddd, J=17.3, 1.5, 1.4 Hz, 1H), 5.29 (ddd, J=10.6, 1.5, 1.4 Hz, 1H), 5.07 (m, 1H), 4.87 (m, 1H), 4.68 (m, 1H), 4.25 (m, 1H), 2.89 (br, 1H), 2.00 (br, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 166.8, 135.9, 133.3, 132.5, 130.1, 129.8, 128.6, 127.9, 118.0, 75.6, 70.3, 61.2. 
         [0151]    Separation conditions for E-15b: OJ-H, 20% IPA, 2.5 mL/min. 67% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   3.136   BV   0.1100    971.22040   138.18152   48.7580       2   3.435   VV   0.1207   1020.70038   134.19174   51.2420            Totals:   1991.92078   272.37326                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 2: DAD1 B, Sig = 235, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 3.168 
                 BV 
                 0.1130 
                 686.64221 
                 94.23962 
                 16.5860 
               
               
                 2 
                 3.473 
                 VV 
                 0.1246 
                 3453.24072 
                 434.97318 
                 83.4140 
               
             
          
           
               
                 Totals: 
                 4139.88293 
                 529.21280 
                   
               
               
                   
               
             
          
         
       
     
       Example 23 
       [0152]    Characterization data for AROCM product Benzoate 15c, 69% isolated yield, 75% Z. Z-15c: [α] D   25 +4.06° (c=0.95, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.09-8.04 (m, 2H), 8.02-7.97 (m, 2H), 7.61-7.54 (2×m, 1H), 7.49-7.39 (2×m, 2H), 6.09-5.96 (3×m, 1H), 5.83-5.78 (m, 1H), 5.67 (dd, J=11.0, 9.7 Hz, 1H), 5.52 (d, J=17.3 Hz, 1H), 5.41 (d, J=10.5 Hz, 1H), 4.56 (ddd, J=13.4, 7.8, 1.4 Hz, 1H), 4.20 (ddd, J=13.4, 5.7, 1.2 Hz, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 166.1, 165.6, 135.4, 133.5, 133.4, 131.8, 130.0, 129.9, 129.85, 129.80, 128.6, 128.6, 125.3, 120.4, 75.6, 71.4, 58.8. HRMS (FAB+) calculated for C 21 H 21 O 5  [M+H]: 353.1389. found 353.1381. 
         [0153]    Separation conditions for Z-15c: OJ-H, 5% IPA, 2.5 mL/min. 96% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   9.799   BV   0.2620   3595.55029   207.71271   50.2636       2   11.027   BB   0.2878   3557.83179   188.87053   49.7364            Totals:   7153.38208   396.58324                        
Enatioenriched 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 9.836 
                 BB 
                 0.2567 
                 6250.97852 
                 370.80807 
                 97.9546 
               
               
                 2 
                 10.889 
                 BB 
                 0.2427 
                 130.52478 
                 6.96354 
                 2.0454 
               
             
          
           
               
                 Totals: 
                 6381.50330 
                 377.77162 
                   
               
               
                   
               
             
          
         
       
     
         [0154]    E-15c. [α] D   25 -1.14° (c=0.56, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.10-7.97 (2×m, 2H), 7.60-7.52 (2×m, 1H), 7.48-7.39 (2×m, 2H), 6.10 (ddd, 15.5, 4.9, 4.8 Hz, 1H), 6.02 (ddd, 17.3, 10.6, 6.4 Hz, 1H), 5.92 (dddd, 15.4, 6.9, 1.7, 1.6 Hz, 1H), 5.84 (m, 1H), 5.80 (m, 1H), 5.49 (d, J=17.2 Hz, 1H), 5.39 (d, J=10.5 Hz, 1H), 4.24-4.18 (m, 2H).  13 C NMR (125 MHz, CDCl 3 ) δ 165.6, 165.5, 135.2, 133.3, 131.8, 130.1, 129.9, 128.6, 128.6, 124.4, 120.1, 75.7, 74.9, 62.8. HRMS (FAB+) calculated for C 21 H 19 O 4  [M−OH]: 335.1283. found 335.1271. 
         [0155]    Separation conditions for E-15c: OJ-H, 5% IPA, 2.5 mL/min. 82% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   12.117   BB   0.2964   2167.36914   110.68974   49.1751       2   13.450   BB   0.3262   2240.08228   102.82623   50.8249            Totals:   4407.45142   213.51597                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 11.841 
                 VV 
                 0.3037 
                 2009.88196 
                 101.20198 
                 90.8688 
               
               
                 2 
                 13.043 
                 BB 
                 0.3044 
                  201.96896 
                 9.96831 
                 9.1312 
               
             
          
           
               
                 Totals: 
                 2211.85092 
                 111.17029 
                   
               
               
                   
               
             
          
         
       
     
       Example 24 
       [0156]    Characterization data for AROCM product Alcohol 15e, 62% isolated yield, 89% Z. Z-15e: [α] D   25 -2.95° (c=0.76, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.37-7.24 (m, 10H), 6.02 (ddd, J=11.1, 6.9, 6.8 Hz, 1H), 5.83 (ddd, J=17.6, 10.4, 7.5 Hz, 1H), 5.56 (dd, J=11.5, 8.9 Hz, 1H), 5.39 (m, 1H), 5.37-5.32 (m, 1H), 4.64 (AB d, J=10.5 Hz, 1H), 4.62 (AB d, J=11.0 Hz, 1H), 4.42 (AB d, J=12.1 Hz, 1H), 4.38 (AB d, J=11.7 Hz, 1H), 4.21 (dd, J=8.6, 7.4, 1.0 Hz, 1H), 4.07-3.93 (2×m, 1H), 3.78 (dd, J=7.2, 7.0 Hz, 1H), 2.13 (br, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 138.2, 137.7, 135.8, 133.7, 131.6, 128.5, 128.4, 128.2, 127.9, 127.8, 127.7, 119.5, 81.5, 76.3, 70.8, 70.7, 58.5. HRMS (FAB+) calculated for C 21 H 25 O 3  [M+H]: 325.1804. found 325.1803. 
         [0157]    Separation conditions for Z-15e: OJ-H, 10% IPA, 2.5 mL/min. 93% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   11.281   BV   0.2773   3639.78735   202.93092   49.9668       2   12.022   VB   0.3028   3644.62769   187.47997   50.0332            Totals:   7284.41504   390.41089                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 11.220 
                 BV 
                 0.2596 
                 210.15450 
                 10.58754 
                 3.5605 
               
               
                 2 
                 11.938 
                 VV 
                 0.3010 
                 5692.16504 
                 295.11295 
                 96.4395 
               
             
          
           
               
                 Totals: 
                 5902.31953 
                 305.70049 
                   
               
               
                   
               
             
          
         
       
     
         [0158]    E-15e. [α] D   25 -2.93° (c=0.30, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.36-7.23 (m, 10H), 5.93-5.79 (2×m, 1H), 5.71 (ddd, J=15.7, 7.5, 7.3 Hz, 1H), 5.33 (m, 1H), 5.29 (m, 1H), 4.65 (AB d, J=12.2 Hz, 1H), 4.62 (AB d, J=12.2 Hz, 1H), 4.47 (AB d, J=12.2 Hz, 1H), 4.43 (AB d, J=12.1 Hz, 1H), 4.18 (m, 2H), 3.90 (dd, J=7.9, 5.6 Hz, 1H), 3.86 (ddd, J=7.4, 4.8, 0.9 Hz, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 138.7, 138.6, 135.6, 133.7, 128.8, 128.4, 127.9, 127.8, 127.6, 127.5, 119.0, 82.5, 81.6, 70.8, 70.7, 63.2. HRMS (FAB+) calculated for C 21 H 25 O 3  [M+H]: 325.1804. found 325.1812. 
         [0159]    Separation conditions for E-15e: OJ-H, 10% IPA, 2.5 mL/min. 86% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                        Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   6.977   BV   0.1991   1499.56213   109.99121   50.4390       2   7.720   VV   0.2202   1473.45618   97.57201   49.5610       Totals:               2973.01831   207.56322                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 7.071 
                 VV 
                 0.2045 
                 342.74240 
                 24.91814 
                 6.9119 
               
               
                 2 
                 7.788 
                 VB 
                 0.2345 
                 4615.99463 
                 288.76001 
                 93.0881 
               
               
                 Totals: 
                   
                   
                   
                 4958.73703 
                 313.67815 
                   
               
               
                   
               
             
          
         
       
     
       Example 25 
       [0160]    Characterization data for AROCM product Benzoate 15f, 61% isolated yield, 88% Z. Z-15f: [α] D   25 -50.9° (c=0.74, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.08-8.02 (m, 2H), 7.60-7.54 (m, 1H), 7.47-7.41 (m, 2H), 7.37-7.22 (m, 10H), 5.97 (dddd, J=11.3, 7.8, 5.8, 1.1 Hz, 2H), 5.85 (ddd, J=17.1, 10.5, 7.5 Hz, 1H), 5.73 (ddd, J=10.7, 9.2, 1.5 Hz, 1H), 5.35-5.33 (m, 1H), 5.31 (m, 1H), 4.87 (ddd, J=13.2, 7.8, 1.4 Hz, 1H), 4.73 (ddd, J=13.2, 5.8, 1.6 Hz, 2H), 4.68 (AB d, J=12.2 Hz 1H), 4.64 (AB d, J=12.1 Hz, 1H), 4.49 (AB d, J=12.1 Hz, 1H), 4.44 (AB d, J=12.2 Hz, 1H), 4.30 (ddd, J=9.1, 5.0, 1.1 Hz, 2H), 3.90 (dd, J=7.5, 5.0 Hz, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 166.4, 138.6, 138.4, 135.5, 133.1, 132.1, 130.2, 129.7, 128.55, 128.50, 128.45, 128.40, 127.8, 127.75, 127.70, 127.5, 119.2, 82.3, 76.7, 70.7, 70.7, 61.2. HRMS (FAB+) calculated for C 28 H 29 O 4  [M+H]: 429.2066. found 429.2056. 
         [0161]    Separation conditions for Z-15f: OJ-H, 20% IPA, 2.5 mL/min. 97% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                        Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   4.059   VV   0.1335   8624.85742    991.43774   49.2384       2   4.842   VB   0.1622   8891.65625    849.16925   50.7616       Totals:               1.75165e4   1840.60699                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 4.088 
                 BV 
                 0.2156 
                 537.15137 
                  38.29383 
                  1.7991 
               
               
                 2 
                 4.857 
                 VB 
                 0.2960 
                 2.93192e4 
                 1527.33167 
                 98.2009 
               
               
                 Totals: 
                   
                   
                   
                 2.98564e4 
                 1565.62550 
               
               
                   
               
             
          
         
       
     
         [0162]    E-15f.  1 H NMR (500 MHz, CDCl 3 ) δ 8.08-8.04 (m, 2H), 7.61-7.54 (m, 1H), 7.45 (m, 2H), 7.36-7.21 (m, 10H), 5.98-5.79 (3×m, 1H), 5.34 (m, 1H), 5.29 (m, 1H), 4.87 (2×m, 1H), 4.64 (AB d, J=12.0 Hz, 2H), 4.47 (AB d, J=12.1 Hz, 1H), 4.43 (AB d, J=12.1 Hz, 1H), 3.92 (dd, J=6.8, 5.3 Hz, 1H), 3.87 (dd, J=6.8, 5.5 Hz, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 166.4, 138.50, 138.42, 135.6, 133.1, 131.8, 130.1, 129.82, 129.80, 128.55, 128.52, 128.44, 128.36, 127.8, 127.60, 127.56, 119.1, 82.4, 81.3, 70.9, 70.6, 64.8. 
         [0163]    Separation conditions for E-15f: OD-H, 20% IPA, 2.5 mL/min. 88% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                        Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   5.665   BV   0.1888   5934.12598   478.10345   49.9106       2   6.250   VB   0.2143   5955.37939   428.19113   50.0894       Totals:               1.18895e4   906.29459                    
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 4.925 
                 BB 
                 0.2038 
                  401.86090 
                  31.71189 
                 4.3113 
               
               
                 2 
                 5.599 
                 BV 
                 0.2213 
                  536.10181 
                  38.78575 
                 5.7514 
               
               
                 3 
                 6.183 
                 VB 
                 0.2409 
                 8383.21680 
                 552.90784 
                 89.9373 
               
               
                 Totals: 
                   
                   
                   
                 9321.17950 
                 623.40548 
               
               
                   
               
             
          
         
       
     
       Example 26 
       [0164]    Characterization data for AROCM product Silyl ether 15g, 68% yield, 87% Z. Initial product mixture derivatized by treatment with TBAF (3 equiv) to aid in purification; isolated product is spectroscopically identical to alcohol 15e. 
         [0165]    Optical rotations and enantiopurity of derivatized products: 
         [0166]    Derivative of Z-15g: [α] D   25 -2.2° (c=0.61, CHCl 3 ) 
         [0167]    89% ee 
         [0000]    Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 11.261 
                 VV 
                 0.3050 
                  316.99796 
                  14.38933 
                 5.7900 
               
               
                 2 
                 11.972 
                 VV 
                 0.3092 
                 5157.96875 
                 262.54877 
                 94.2100 
               
               
                 Totals: 
                   
                   
                   
                 5474.96671 
                 276.93809 
               
               
                   
               
             
          
         
       
     
         [0168]    Derivative of E-15g:[α] D   25 -3.4°(c=0.31, CHCI 3 ) 
         [0169]    77% ee 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 7.070 
                 VV 
                 0.2254 
                 329.41394 
                 21.65948 
                 11.2280 
               
               
                 2 
                 7.819 
                 VB 
                 0.2454 
                 2604.45679 
                 157.07635 
                 88.7720 
               
               
                 Totals: 
                   
                   
                   
                 2933.87073 
                 178.73583 
                   
               
               
                   
               
             
          
         
       
     
       Example 27 
       [0170]    Characterization data for AROCM product Benzyl ether 15h, 64% isolated yield, 86% Z. Z-15h: [α] D   25 -29.7° (c=0.66, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.36-7.23 (m, 10H), 5.91 (dddd, J=11.4, 7.3, 5.4, 1.1 Hz, 1H), 5.83 (ddd, J=17.2, 10.4, 7.6 Hz, 1H), 5.61 (dddd, J=11.0, 9.2, 1.7, 1.6 Hz, 1H), 5.34-5.30 (m, 1H), 5.28 (m, 1H), 4.64 (AB d, J=12.2 Hz, 1H), 4.61 (AB d, J=12.1 Hz, 1H), 4.43 (AB d, J=12.2 Hz, 1H), 4.43-4.41 (2×AB d, 1H), 4.40 (AB d, J=12.1 Hz, 1H), 4.16 (ddd, J=9.2, 4.9, 1.1 Hz, 1H), 4.04 (ddd, J=12.6, 7.3, 1.6 Hz, 1H), 3.93 (ddd, J=12.6, 5.4, 1.8 Hz, 1H), 3.82 (dddd, J=7.6, 5.0, 1.2, 0.9 Hz, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 138.6, 138.5, 138.3, 135.5, 131.6, 130.3, 128.52, 128.39, 128.36, 127.84, 127.81, 127.77, 127.76, 127.56, 127.53, 119.1, 82.5, 76.4, 72.5, 70.6, 70.4, 66.4. HRMS (FAB+) calculated for C 28 H 31 O 3  [M+H]: 415.2273. found 415.2260. 
         [0171]    Separation conditions for Z-15h: OD-H, 15% IPA, 2.5 mL/min. 91% ee 
         [0000]    Racemate: 

 
         [0000]                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1   7.714   BB   0.2523   3691.89014   233.73363   49.8466       2   8.793   VB   0.2827   3714.60791   205.71669   50.1534       Totals:               7406.49805   439.45032                    
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 7.739 
                 BV 
                 0.2524 
                 6725.33252 
                 416.38754 
                 95.2967 
               
               
                 2 
                 8.821 
                 VB 
                 0.2569 
                  331.92462 
                  18.54005 
                 4.7033 
               
               
                 Totals: 
                   
                   
                   
                 7057.25714 
                 434.92760 
               
               
                   
               
             
          
         
       
     
       Example 28 
       [0172]    Characterization data for AROCM product 15i. Isolated as an inseparable 9:1 Z/E mixture, 76% yield. Z-15i:  1 H NMR (500 MHz, CDCl 3 ) δ 7.38-7.25 (m, 10H), 7.06-7.00 (m, 2H), 6.79-6.75 (m, 2H), 5.95-5.82 (2×m, 1H), 5.54 (ddd, J=11.0, 9.4, 1.7, 1.5 Hz, 1H), 5.37 (m, 1H), 5.29 (m, 1H), 4.67 (2×AB d, J=12.2 Hz, 2H), 4.49 (AB d, J=12.2 Hz, 1H), 4.47 (AB d, J=12.1 Hz, 1H), 4.36 (ddd, J=9.3, 4.8, 1.1 Hz, 1H), 3.89 (dd, J=7.7, 4.9 Hz, 1H), 3.78 (s, 3H), 3.34-3.20 (m, 2H).  13 C NMR (125 MHz, CDCl 3 ) δ 158.0, 138.77, 138.76, 135.7, 133.9, 132.4, 129.63, 129.45, 128.4, 128.0, 127.84, 127.78, 127.53, 127.49, 119.0, 114.0, 82.7, 76.3, 70.6, 70.3, 55.4, 33.4. HRMS (FAB+) calculated for C 28 H 31 O 3  [M+H]: 415.2273. found 415.2287. 
         [0173]    Separation conditions for Z/E product mixture: AD-H, 10% IPA, 2.5 mL/min. Z: 93% ee; E: 79% ee. 
         [0000]    Racemate: 

 
         [0000]                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %               1    9.466   VB   0.2176   4234.35059   305.74072   44.0459       2   10.421   BV   0.2378   4251.52734   279.00278   44.2245       3   10.869   VV   0.2464    545.18933    34.12083    5.6711       4   12.217   VV   0.2952    582.43701    31.58193    6.0585       Totals:               9613.50427   650.44626                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                  8.802 
                 BV 
                 0.2556 
                 2.11839e4 
                 1345.92456 
                 85.3335 
               
               
                 2 
                  9.623 
                 VV 
                 0.2273 
                 735.39277 
                  48.94960 
                  2.9623 
               
               
                 3 
                  9.977 
                 VB 
                 0.2593 
                 298.80161 
                  16.18907 
                  1.2036 
               
               
                 4 
                 11.232 
                 BV 
                 0.2637 
                 2606.73169 
                  152.29791 
                 10.5005 
               
               
                 Totals: 
                   
                   
                   
                 2.48248e4 
                 1563.36114 
                   
               
               
                   
               
             
          
         
       
     
       Example 29 
       [0174]    Characterization data for AROCM Ketone 15j, 65% isolated yield, 90% Z. Z-15j: [α] D   25 -7.98° (c=1.35, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.39-7.22 (m, 10H), 5.86 (ddd, J=17.2, 10.4, 7.6 Hz, 1H), 5.65 (dtd, J=11.1, 7.5, 1.0 Hz, 1H), 5.46 (ddt, J=10.9, 9.3, 1.6 Hz, 1H), 5.35 (m, 1H), 5.27 (m, 1H), 4.66 (AB d, J=12.1 Hz, 1H), 4.61 (AB d, J=12.2 Hz, 1H), 4.45 (AB d, J=12.1 Hz, 1H), 4.43 (AB d, J=12.2 Hz, 1H), 4.23 (ddd, J=9.3, 5.0, 1.0 Hz, 1H), 3.84 (dd, J=7.6, 5.0, 1H), 2.38 (m, 2H), 2.24 (m, 2H), 2.04 (s, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 208.0, 138.753, 138.746, 135.7, 133.2, 128.6, 128.36, 128.34, 127.81, 127.75, 127.51, 127.49, 118.9, 82.6, 76.3, 70.6, 70.3, 43.3, 30.0, 22.3. HRMS (FAB+) calculated for C 24 H 29 O 3  [M+H]: 365.2117. found 365.2113. 
         [0175]    Separation conditions for Z-15j: OJ-H, 5% IPA, 2.5 mL/min. 92% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                        Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   9.787   BV   0.3728   4472.42529   180.68672   49.6322       2   10.883   VBA   0.4203   4538.71436   163.26811   50.3678       Totals:               9011.13965   343.95483                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
               
                 1 
                  9.565 
                 BB 
                 0.2466 
                  294.21240 
                  18.00591 
                  3.8669 
               
               
                 2 
                 10.607 
                 BB 
                 0.2664 
                 7314.22949 
                 405.54443 
                 96.1331 
               
               
                 Totals: 
                   
                   
                   
                 7608.44189 
                 423.55034 
               
               
                   
               
             
          
         
       
     
         [0176]    E/Z-15j mixture: 

 
         [0000]                                                                                        Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   9.874   BB   0.2847   2521.13306   133.25986   16.6689       2   10.986   BV   0.3148   2570.48706   123.50429   16.9952       3   11.655   VB   0.3314   5003.31738   226.75299   33.0803       4   12.990   BB   0.3684   5029.84863   206.30301   33.2557       Totals:               1.51248e4   689.82014                        
Enantioenriched: E84% ee. 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                  9.616 
                 BV 
                 0.2410 
                 174.28995 
                 10.11655 
                  1.9790 
               
               
                 2 
                 10.689 
                 VV 
                 0.2750 
                 3897.29248 
                 211.45294 
                 44.2520 
               
               
                 3 
                 11.391 
                 VB 
                 0.2866 
                 379.96729 
                 19.56160 
                  4.3144 
               
               
                 4 
                 12.698 
                 BV 
                 0.3234 
                 4355.48779 
                 202.13602 
                 49.4546 
               
             
          
           
               
                 Totals: 
                 8807.03751 
                 443.26711 
                   
               
               
                   
               
             
          
         
       
     
       Example 30 
       [0177]    Characterization data for AROCM Boronic ester 15k, 50% isolated yield of Z product. [α] D   25  7.98° (c=0.64, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.37-7.28 (m, 10H), 5.94-5.78 (2×m, 1H), 5.43 (dddd, J=11.0, 9.3, 1.7, 1.5 Hz, 1H), 5.28 (m, 1H), 5.25 (m, 1H), 4.67 (AB d, J=12.2 Hz, 1H), 4.64 (AB d, J=12.3 Hz, 1H), 4.47 (AB d, J=12.4 Hz, 1H), 4.44 (AB d, J=12.2 Hz, 1H), 4.30 (ddd, J=9.4, 4.0, 1.1 Hz, 1H), 3.88 (dd, J=7.7, 4.0 Hz, 1H), 1.69 (m, 2H), 1.23 (s, 6H), 1.22 (s, 6H).  13 C NMR (125 MHz, CDCl 3 ) δ 139.1, 139.0, 135.7, 130.0, 128.31, 128.30, 127.7, 127.6, 127.34, 127.33, 126.9, 118.8, 83.5, 82.8, 76.2, 70.5, 70.1, 24.94, 24.93. HRMS (FAB+) calculated for C 20 H 28 O 3 B [M-OBn]: 327.2132. found 327.2138. 
         [0178]    Separation conditions for Z-15k: OJ-H, 5% IPA, 2.5 mL/min. 91% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   4.784   BV   0.2705   4108.72510   219.40474   55.4931       2   7.295   VB   0.3813   3295.29712   132.87819   44.5069            Totals:   7404.02222   352.28293                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 4.898 
                 BV 
                 0.1625 
                 331.67175 
                 30.59655 
                 4.2149 
               
               
                 2 
                 5.190 
                 VV 
                 0.2376 
                 402.79446 
                 23.30932 
                 5.1187 
               
               
                 3 
                 7.472 
                 VV 
                 0.2806 
                 7134.57031 
                 384.21341 
                 90.664 
               
             
          
           
               
                 Totals: 
                 7869.03653 
                 438.11928 
                   
               
               
                   
               
             
          
         
       
     
       Example 31 
       [0179]    Characterization data for AROCM Alcohol 17. Alcohol 17 was synthesized following the general AROCM procedure in 85% isolated yield, 91% Z, and 1:1 dr. Z-17:  1 H NMR (500 MHz, CDCl 3 ) δ 7.36-7.24 (m, 10H), 5.89-5.78 (2×m, 1H), 5.54-5.43 (dddd, J=11.1, 9.8, 1.3, 1.0 Hz, 1H), 5.38 (m, 1H), 5.32 (m, 1H), 4.66 (AB d, J=12.3 Hz, 2H), 4.59 (AB d, J=12.2 Hz, 2H), 4.41 (AB d, J=12.4 Hz, 2H), 4.38 (AB d, J=12.1 Hz, 2H), 4.20 (ddd, J=9.8, 6.9, 0.9 Hz, 2H), 3.78 (dd, J=7.7, 6.9 Hz, 1H), 3.74 (m, 1H), 2.81 (br, 1H), 2.18-2.10 (m, 2H), 1.16 (d, J=6.2 Hz, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 138.5, 137.9, 135.9, 131.8, 131.1, 128.40, 128.37, 128.2, 127.82, 127.75, 127.6, 119.7, 81.2, 75.6, 70.23, 70.18, 66.9, 38.1, 23.2. HRMS (FAB+) calculated for C 23 H 29 O 3  [M+H]: 353.2117. found 353.2108. 
       Example 32 
       [0180]    Ketone 18: Dess-Martin periodinane (302 mg, 0.713 mmol, 2 equiv) was added in one portion to a cold (0° C.) solution of alcohols Z-17 (126 mg, 0.356 mmol) in CH 2 Cl 2  (5 mL). The reaction mixture was allowed to warm to room temperature and stirred for 1 h. Aqueous 1:1 NaHCO 3 /Na 2 S 2 O 3  solution was added and the biphasic mixture stirred vigorously for 1 h. The layers were separated, and the aqueous layer extracted with CH 2 Cl 2 . The combined organic layers were dried over MgSO 4 , filtered and concentrated. The crude residue was purified by flash chromatography to afford 110.4 mg, 88% yield of ketone 18. [α] D   25 -14.4° (c=0.83, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.36-7.24 (m, 10H), 5.93 (dddd, J=11.1, 10.8, 7.2, 1.1 Hz, 1H), 5.85 (ddd, J=17.2, 10.4, 7.6 Hz, 1H), 5.63 (dddd, J=11.0, 9.1, 1.7, 1.4 Hz, 1H), 5.36-5.33 (m, 1H), 5.33-5.27 (m, 1H), 4.63 (2×ABd, J=12.0 Hz, 2H), 4.43 (AB d, J=10.8 Hz, 1H), 4.39 (AB d, J=Hz, 1H), 4.09 (ddd, J=9.1, 5.2, 1.1 Hz, 1H), 3.84 (dd, J=7.6, 5.3 Hz, 1H), 3.08 (dd, J=7.2, 1.7 Hz, 2H), 2.03 (s, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 206.1, 138.6, 138.4, 135.6, 130.7, 128.40, 128.37, 127.87, 127.86, 127.62, 127.58, 126.4, 119.1, 82.4, 76.3, 70.7, 70.3, 42.7, 29.8. HRMS (FAB+) calculated for C 23 H 27 O 3  [M+H]: 351.1960. found 351.1954. 
         [0181]    Separation conditions for 18: AD-H, 5% IPA, 2.5 mL/min. 95% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   7.509   VV   0.1535   2803.53540   288.06458   49.4751       2   7.938   VV   0.1670   2863.01855   262.90552   50.5249            Totals:   5666.55396   550.97009                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 7.548 
                 BV 
                 0.1477 
                 159.29933 
                 16.64186 
                 2.4029 
               
               
                 2 
                 7.911 
                 VV 
                 0.1731 
                 6470.11279 
                 584.80743 
                 97.5971 
               
             
          
           
               
                 Totals: 
                 6629.41212 
                 601.44930 
                   
               
               
                   
               
             
          
         
       
     
       Example 33 
       [0182]    (+)-endo-brevicomin (19). Ketone 18 (35 mg, 0.10 mmol) was dissolved in 5:1 MeOH/1 N HCl (aq.) and the reaction flask purged with Argon. Palladium on carbon (10%, 35 mg) was added, and the flask was purged by a balloon filled with H 2 . The reaction mixture was stirred under 1 atm of H 2  for 2 h. The reaction flask was then purged with Argon and Celite was added. The suspension was filtered through Celite and the organic layer was extracted with pentane. The combined pentane layers were washed with water, brine, and dried over MgSO 4 . The pentane layers were filtered and carefully concentrated to afford the crude reaction mixture (9.9 mg, 67% yield), containing 90% purity (+)-endo-brevicomin Analytical samples were afforded by flash chromatography. [α] D   25 +49.6° (c=0.11, CHCl 3 ), lit. (see G. Pedrocchi-Fantoni, S. Servi,  J. Chem. Soc., Perkin. Trans.  1 1991, 1764. [α] D   20 +49° (c=1.0, ether, 96.5% ee, 90% purity), lit. (see S. Singh, P. J. Guiry,  J. Org. Chem.  2009, 74, 5758). [α] D   20  77.9° 9 (c=1.2, ether, 99.3% ee);  1 H NMR (500 MHz, CDCl 3 ) δ 4.21 (dt, J=4.6, 2.3 Hz, 1H), 3.99 (tdd, J=7.2, 4.1, 1.0 Hz, 1H), 1.99-1.72 (m, 4H), 1.68-1.51 (m, 4H), 1.43 (s, 3H), 0.99 (t, J=7.5 Hz, 3H).  13 C NMR (125 MHz, CDCl 3 ) δ 107.0, 81.6, 76.6, 34.4, 25.0, 23.6, 21.9, 17.6, 10.9. HRMS (FAB+) calculated for C 9 H 17 O 2  [M+H]: 157.1229. found 157.1206. 
         [0183]    Separation conditions (GC, GTA column): 80° C., isocratic. 96% ee 
         [0000]    Racemate: 

 
         [0000]                                                    Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [pA*s]   [pA]   %                   1   8.063   BB   0.1233   30.86736   3.62755   50.14859       2   8.646   BB   0.1302   30.68445   3.27842   49.85141                    
Enantioenriched: 

 
         [0000]    
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [pA*s] 
                 [pA] 
                 % 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 8.098 
                 BB 
                 0.1045 
                 2.60984 
                  3.18731e−1 
                 1.90416 
               
               
                 2 
                 8.656 
                 BB 
                 0.1424 
                 120.87816 
                 12.66055 
                 88.19333 
               
               
                 3 
                 9.918 
                 BB 
                 0.116 
                 13.57243 
                  1.55830 
                 9.90251 
               
               
                   
               
             
          
         
       
     
       Example 34 
       [0184]    Diol 20. To a biphasic mixture of 1:1 tBuOH/water containing diene Z-15g (38.5 mg, 0.089 mmol) was sequentially added potassium carbonate (37 mg, 0.27 mmol), potassium ferricyanide (89 mg, 0.27 mmol, 3 equiv), and potassium osmate dihydrate (1.7 mg, 4.6 μmol, 5 mol %) at 0° C. The reaction was stirred vigorously at 23° C. for 24 h. Upon completion, solid Na 2 SO 3  was added stirred continued at 23° C. for 2 h. EtOAc was added and the layers separated. The aqueous layer was extracted with EtOAc and the combined organic layers washed with water, brine, and dried over MgSO 4 . After filtration and concentration, the crude residue was subject to flash chromatography to afford 27.5 mg, 66% yield of diol 20. 
         [0185]    Major diastereomer: [α] D   25 -62.1° (c=1.35, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 8.05-8.01 (m, 2H), 7.60-7.55 (m, 1H), 7.44 (dd, J=8.5, 7.2 Hz, 2H), 7.37-7.22 (m, 26H), 6.05-5.97 (m, 1H), 5.86-5.78 (m, 1H), 4.89-4.83 (m, 2H), 4.77 (d, J=11.1 Hz, 1H), 4.67 (d, J=11.8 Hz, 1H), 4.65-4.62 (m, 1H), 4.60 (dd, J=9.6, 4.6 Hz, 1H), 4.45 (d, J=11.7 Hz, 1H), 3.72 (dt, J=13.1, 5.0 Hz, 4H).  13 C NMR (125 MHz, CDCl 3 ) δ 166.6, 138.1, 137.8, 133.3, 131.3, 129.87, 128.78, 128.65, 128.62, 128.58, 128.3, 128.02, 128.01, 128.0, 80.9, 76.1, 74.6, 72.1, 70.8, 66.3, 63.7, 61.2. HRMS (FAB+) calculated for C 28 H 31 O 6  [M+H]: 463.2121. found 463.2125. 
       Example 35 
       [0186]    Methyl glycoside 21. Diol 20 (34.6 mg, 0.075 mmol) was dissolved in 1:1 CH 2 Cl 2 /MeOH and cooled to −78° C. Ozone was bubbled through the solution until a blue color persisted for 10 min. At this point, oxygen was bubbled through the solution until the reaction appeared colorless. Excess dimethyl sulfide (0.1 mL) was added and the reaction was allowed to come to room temperature and stir for 16 h. The reaction mixture was concentrated and the crude residue used in the following step. The crude aldehyde was then dissolved in MeOH (5 mL) and cooled to 0° C. HCl in MeOH (0.4 M, 0.5 mL) was added and the reaction was warmed to room temperature. The reaction was stirred for 14 h, at which time Amberlyst IRA-400 (OH − ) was added. The mixture was filtered and concentrated; preparative TLC afforded 10.6 mg (0.031 mmol, 47% yield over two steps) of methyl glycoside 21. [α] D   25 =−36.4° (c=0.27, CHCl 3 ), lit (see P. A. Wender, F. C. Bi, N. Buschmann, F. Gosselin, C. Kan, J-M. Kee, H. Ohmura,  Org. Lett.  2006, 8, 5373). ent-21 [α] D   25 =+31.7 (c=1.94, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.40-7.27 (m, 10H), 4.89 (s, 1H), 4.66 (AB d, J=12.0 Hz, 1H), 4.63 (AB d, J=12.0 Hz, 1H), 4.58 (AB d, J=11.7 Hz, 1H), 4.49 (AB d, J=11.7 Hz, 1H), 4.28 (m, 1H), 4.13 (dd, J=7.1, 4.7 Hz, 1H), 3.87 (d, J=4.7 Hz, 1H), 3.83-3.77 (m, 1H), 3.58 (m, 1H), 3.37 (s, 3H), 1.95 (br, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 137.81, 137.79, 128.6, 128.1 (4C), 128.04 (3C), 128.00 (3C), 107.0, 82.4, 80.3, 77.4, 72.8, 72.6, 62.8, 55.7. HRMS (FAB+) calculated for C 20 H 23 O 5  [M+H−H 2 ]: 343.1545. found 343.1553. 
       General Procedure for Preparation of Silver Carboxylates 
       [0187]    Following a known procedure (see Dorta, R.; Shimon, L.; Milstein, D.  J. Organomet. Chem.  2004, 689, 751-758) L-N-acetyl alanine (200 mg, 1.53 mmol, 2 equiv.) was added to a stirring suspension of silver oxide (177 mg, 0.762 mmol, 1 equiv.) in 4 mL acetonitrile shielded from light. The reaction was vigorously stirred for 24 h, at which time a light gray precipitate had formed. The mixture was filtered and washed with acetonitrile and ether. The resultant solid was dried under vacuum overnight while shielded from light to provide 212 mg (0.89 mmol, 58% yield) of silver carboxylate. 
       General Procedure for Preparation of Catalysts 22a-h 
       [0188]    To a solution of enantiopure ruthenium iodide 1 (1.92 mg, 0.0028 mmol) in 0.5 mL THF was added silver carboxylate from above (1.3 mg, 0.055 mmol, 2 equiv.). The mixture was stirred for 30 min and then concentrated. The resultant solid was redissolved in benzene and filtered through a short pad of Celite. The resultant purple solution was concentrated, assayed by  1 H NMR and then used directly in the AROCM reaction.  1 NMR spectra of complexes 22a-c matched previously reported spectra of the corresponding racemic complexes (see Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H.  J. Am. Chem. Soc.,  2012, 134, 693-699). Diagnostic benzylidene signals (C 6 D 6 ) of novel compounds are listed below: 
         [0000]    22d: 14.99 ppm
 
22e: 15.00 ppm
 
22f: 15.10 ppm
 
22h: 15.11 ppm
 
       Preparation of Substrates for AROCM 
       [0189]    Substrates for AROCM were synthesized as previously reported in the literature: 23 (see Coe, J. W.; Wirtz, M. C.; Bashore, C. G.; Candler, J.  Org. Lett.  2004, 6, 1589-1592) and 25 (See La, D. S.; Sattely, E. S.; Ford, J. G.; Schrock, R. R.; Hoveyda, A. H.  J. Am. Chem. Soc.  2001, 123, 7767-7778) were synthesized according to the provided references. 
       General Procedure for AROCM 
       [0190]    In a glovebox, alkene 25 (40 mg, 0.2 mmol, 1 equiv) and allyl acetate (6) (140 mg, 1.4 mmol, 7 equiv) were dissolved in 0.4 mL THF. To this solution was added catalyst 4 (1.27 mg, 0.002 mmol). The reaction vial was capped and stirred for 1 h and then quenched with an excess of ethyl vinyl ether. The reaction mixture was concentrated and conversion was determined by 500 MHz  1 H NMR. The crude was subjected to flash chromatography or preparative TLC to afford the desired AROCM product (26, 33 mg, 56% yield, 15:85 Z/E ratio, 94% ee (Z), 93% ee (E)). Pure products were submitted to analytical SFC to determine ee. 
       Example 36 
       [0191]    Characterization data for AROCM product 24, 55% yield, 76:14 Z/E ratio. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0192]    Z-24:  1 H NMR (500 MHz, CDCl 3 ) δ 7.25-7.20 (m, 2H), 7.19-7.14 (m, 1H), 7.11-7.07 (m, 1H), 5.89-5.81 (m, 1H), 5.80-5.75 (m, 1H), 5.67 (ddd, J=10.7, 9.6, 1.1 Hz, 1H), 5.25 (ddd, J=17.0, 1.9, 1.0 Hz, 1H), 5.18 (dd, J=10.0, 1.8 Hz, 1H), 4.78 (dt, J=6.9, 1.0 Hz, 2H), 4.15-4.03 (m, 1H), 3.76 (dt, J=10.3, 7.7 Hz, 1H), 2.54 (dt, J=12.3, 7.0 Hz, 1H), 2.11 (d, J=0.8 Hz, 2H), 1.64 (dt, J=12.2, 10.5 Hz, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 145.72, 145.25, 140.55, 137.57, 127.04, 124.77, 124.30, 124.12, 116.02, 60.59, 49.13, 42.79, 41.59, 21.16. HRMS (FAB+) calculated for C 16 H 17 O 2  [M+H−H 2 ]: 241.1229. found 241.1221. 
         [0193]    Separation conditions: AD-H, 3% IPA, 2.5 mL/min &gt;98% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   3.503   BV   0.1472   6139.82520   668.11780   49.9774       2   3.826   VB   0.1547   6145.36768   625.22028   50.0226            Totals:     1.22852e4   1293.33807                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
               
                 1 
                 3.907 
                 BB 
                 0.2003 
                 1.85037e4 
                 1456.06311 
                 100.0000 
               
             
          
           
               
                 Totals: 
                 1.85037e4 
                 1456.06311 
                   
               
               
                   
               
             
          
         
       
     
         [0000]    
       
                 
         
             
             
         
       
     
         [0194]    E-24 was deacetylated to the compound shown above in order to aid purification. 
         [0195]      1 H NMR (# MHz, CDCl 3 ) δ 7.25-7.10 (m, 3H), 5.91-5.79 (m, 2H), 5.77-5.69 (m, 1H), 5.22 (ddd, J=17.1, 1.8, 0.9 Hz, 1H), 5.15 (dd, J=10.0, 1.9 Hz, 1H), 4.20 (t, J=5.7 Hz, 2H), 3.73 (dq, J=16.8, 8.3 Hz, 2H), 2.52 (dt, J=12.4, 7.1 Hz, 1H), 1.66 (dt, J=12.4, 10.3 Hz, 1H), 1.32 (t, J=5.7 Hz, 1H). 
         [0196]    Separation conditions: AD-H, 3% IPA, 2.5 mL/min &gt;98% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   12.963   BV   0.3805   1630.66382   52.19287   49.3447       2   13.901   VV   0.4567   1673.97461   49.73441   50.6553            Totals:   3304.63843   101.92728                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 14.509 
                 VB 
                 0.5751 
                 4652.46533 
                 130.76849 
                 100.0000 
               
             
          
           
               
                 Totals: 
                 4652.46533 
                 130.76849 
                   
               
               
                   
               
             
          
         
       
     
       Example 37 
       [0197]    Characterization data for AROCM product 26, 56% yield, 15:85 Z/E ratio. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0198]    Z-26 [α] D   25 =−23.9° (c=0.21, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.35-7.24 (m, 5H), 5.99 (ddd, J=17.1, 10.2, 8.2 Hz, 1H), 5.90-5.83 (m, 1H), 5.55 (dtd, J=11.1, 7.0, 1.0 Hz, 1H), 5.08 (ddd, J=17.2, 2.1, 1.0 Hz, 1H), 5.02 (ddd, J=10.2, 2.0, 0.8 Hz, 1H), 4.62 (dt, J=7.1, 1.1 Hz, 2H), 4.55 (d, J=11.7 Hz, 1H), 4.50 (d, J=11.7 Hz, 1H), 3.76 (t, J=4.1 Hz, 1H), 2.91 (qd, J=9.1, 4.3 Hz, 1H), 2.62 (qd, J=8.6, 3.9 Hz, 1H), 2.06 (s, 2H), 1.82 (dq, J=9.4, 6.9 Hz, 3H), 1.75-1.67 (m, 1H).  13 C NMR (125 MHz, CDCl 3 ) δ 139.25, 139.09, 136.26, 128.34, 127.74, 127.52, 123.45, 115.04, 86.93, 73.76, 60.77, 50.32, 43.45, 30.53, 30.11, 28.99, 21.14. HRMS (FAB+) calculated for C 19 H 24 NaO 3  [M+Na]: 323.1623. found 323.1627. 
         [0199]    Separation conditions: OJ-H, 1% IPA, 2.5 mL/min. 94% ee 
         [0000]    Racemate: 

 
         [0000]                                                                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU*s]   [mAU]   %                    1   11.035   BV   0.2512   2302.19849   137.56712   50.2543       2   11.905   VV   0.2763   2278.89893   127.66735   49.7457            Totals:   4581.09741   265.23447                        
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360,100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU*s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 11.301 
                 BV 
                 0.2214 
                 239.09720 
                 13.58221 
                 2.6496 
               
               
                 2 
                 12.062 
                 VB 
                 0.3154 
                 8784.66992 
                 414.32910 
                 97.3504 
               
             
          
           
               
                 Totals: 
                 9023.76712 
                 427.91131 
                   
               
               
                   
               
             
          
         
       
     
         [0000]    
       
                 
         
             
             
         
       
     
         [0200]    E-26 [α] D   25 =−1.1° (c=0.67, CHCl 3 );  1 H NMR (500 MHz, CDCl 3 ) δ 7.40-7.23 (m, 5H), 6.07-5.97 (m, 1H), 5.95-5.88 (m, 1H), 5.61 (dt, J=15.8, 6.4 Hz, 1H), 5.09 (d, J=17.3 Hz, 1H), 5.03 (dd, J=10.4, 1.9 Hz, 1H), 4.57 (d, J=11.9 Hz, 1H), 4.54-4.51 (m, 2H), 4.49 (dd, J=11.8, 1.5 Hz, 1H), 3.79 (t, J=4.3 Hz, 1H), 2.62 (dt, J=9.7, 4.6 Hz, 2H), 2.05 (d, J=1.5 Hz, 3H), 1.87-1.75 (m, 4H).  13 C NMR (125 MHz, CDCl 3 ) δ 139.37, 139.10, 136.73, 128.31, 127.82, 127.53, 124.18, 114.96, 86.98, 73.70, 65.35, 50.14, 48.54, 28.91, 21.11. HRMS (FAB+) calculated for C 19 H 24 NaO 3  [M+Na]: 323.1623. found 323.1628. 
         [0201]    Separation conditions: AD-H, 2% IPA, 2.5 mL/min. 93% ee 
         [0000]    Racemate 

 
         [0000]                                                          Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100            Peak   RetTime       Width   Area   Height   Area       #   [min]   Type   [min]   [mAU * s]   [mAU]   %               1   5.781   VV   0.2561   3036.30420   188.30795   50.6709       2   6.350   VV   0.2732   2955.90186   174.83788   49.3291       Totals:               5992.20605   363.14583                    
Enantioenriched: 

 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Signal 1: DAD1 A, Sig = 210, 8 Ref = 360, 100 
               
             
          
           
               
                 Peak 
                 RetTime 
                   
                 Width 
                 Area 
                 Height 
                 Area 
               
               
                 # 
                 [min] 
                 Type 
                 [min] 
                 [mAU * s] 
                 [mAU] 
                 % 
               
               
                   
               
             
          
           
               
                 1 
                 5.659 
                 VV 
                 0.2846 
                 596.53467 
                 32.73715 
                 3.5544 
               
               
                 2 
                 6.433 
                 VV 
                 0.3100 
                  1.61865e4 
                 850.61707 
                 96.4456 
               
               
                 Totals: 
                   
                   
                   
                  1.67830e4 
                 883.35422