bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of 1,2,3,4‐Bisiminofullerene and 1,2,3,4‐Bis(triazolino)fullerene—on the Mechanism of the Addition Reactions of Organic Azides to [60]Fullerene
Authors: Shen Clifton K.‐F. , Yu Hsiao‐Hua , Juo Chiun‐Gung , Chien Kuo‐Ming , Her Guor‐Rong , Luh Tien‐Yau 
Published: July 2007

AbstractThe reactions of organic azides with [60]fullerene have paved the way for the synthesis of adducts with a variety of structures. Treatment of [60]fullerene with 2,2‐dibenzyl‐1,3‐diazidopropane (10) in refluxing chlorobenzene afforded three products, namely, 8, 9, and 11 in 18, 25, and 11% yields, respectively. Thermolysis of 9a in refluxing chlorobenzene gave a 40:54:6 mixture of 8, 11, and C60 in quantitative yield. No interconversion between 8 and 11 was observed. Whereas 11 was stable towards thermolysis, 8 decomposed to C60 (35% yield) on refluxing in chlorobenzene for 24 h, but it did not produce any 11. This indicates that 9a is an intermediate in the formation of 8 and 11. A general mechanism for the addition of azides to C60 is proposed. A similar mechanistic pathway is suggested for the thermolysis of 9a.
Stereoselective Umpolung Reactions with MetalatedP‐Chiral Cyanohydrin Phosphates—Enantioselective Synthesis of Tertiary Cyanohydrins
Authors: Schrader Thomas 
Published: July 2007

AbstractWe present the first cyanohydrin derivative4that allows diastereoselective umpolung reactions. In4the OH group of the cyanohydrin is linked with a chiral phosphate, which can be removed hydrolytically after asymmetric synthesis. Cyclization of pseudoephedrine1dwith POCl3gave2d. This was followed by addition of racemic benzaldehyde cyanohydrin3to give the key intermediate4dwith complete retention of the configuration at phosphorus. Deprotonation of4d, followed by addition of a wide variety of electrophiles afforded the crystalline products5with high diastereomeric excesses (deup to 94%). High asymmetric induction was also achieved for the reaction of4−Li+with acyl halides, α‐bromoacetates, 2‐cycloalkenones, α,β‐unsaturated esters, and γ‐bromoacetates. Lewis acid assisted hydrolysis proceeded without racemization and gave high yields of ketone cyanohydrins6. From the ring‐opened chiral auxiliary7, optically pure pseudoephedrine1was readily recovered by acid hydrolysis. Optically pure (R) and (S) ketone cyanohydrins are now accessible in a very general strategy, which circumvents the substrate limitations of enzymatic synthesis.
Self‐Assembly of Dinuclear CH2‐bridged Titanium(IV)/Catecholate Complexes: Influence of the Counterions and of Methyl Substituents in the Ligand
Authors: Albrecht Markus 
Published: July 2007

AbstractThe spontaneous self‐assembly of methylene‐bridged dinuclear TiIV complexes M4[L3Ti2] (L = 1–3) from CH2‐bridged di(catechol) ligands (1‐H4–3‐H4) was found to proceed in the presence of lithium or sodium carbonate acting as a base (M = Li, Na). In contrast, only an unspecific mixture of coordination compounds was obtained in the presence of potassium carbonate. This difference in behavior is due to the ability of Li+ or Na+ to stabilize the triple‐stranded dinuclear titanium(IV) species [L3Ti2]4‐. In the solid state, Li4[(1)3Ti2] exhibits a highly symmetric structure with three lithium cations bound to the meso‐helicate tetraanion. 6Li NMR together with 1H NMR studies at variable temperature revealed that, in solution, an unsymmetrical „bowl‐shaped”︁ species is formed with only two Li+ bound to the anion. A methyl substituent on the methylene spacer of the di(catechol) ligand (ligand 2) led to supramolecular systems with new stereocenters and thus a higher content of information. However, only one of the four possible diastereoisomeric metal complexes of [(2)3Ti2]4‐ was observed. A third type of ligand, with a methyl group attached to one terminus of the linear ligand, was also investigated. The synthesis of such an unsymmetrical ligand, 3‐H4, was readily achieved starting from 2,3‐dimethoxyben‐zyl alcohol (4) and 2,3‐dimethoxybenz‐aldehyde (6). Upon complexation, the ligand 3‐H4 led to a statistical mixture of the two possible isomers of the dinuclear titanium(IV) complex [(3)3Ti2]4‐.
Poly(triacetylene) Oligomers: Synthesis, Characterization, and Estimation of the Effective Conjugation Length by Electrochemical, UV/Vis, and Nonlinear Optical Methods
Authors: Martin Rainer E. , Günter Peter , Bosshard Christian , Gubler Ulrich , Gramlich Volker , Gross Maurice , Boudon Corinne , Gisselbrecht Jean‐Paul , Diederich François 
Published: July 2007

AbstractPoly(triacetylene)s [PTAs, (CCCRCRCC)n–] are a new class of linearly conjugated polymers with a nonaromatic all‐carbon backbone. To explore structure–property relationships in PTAs, we prepared a series of monodisperse oligomers ranging from monomer to hexamer by oxidative Glaser–Hay coupling of a bifunctional („chain‐forming”︁) (E)‐hex‐3‐ene‐1,5‐diyne in the presence of an endcapping unit. All six oligomers are amazingly stable towards exposure to light, air, and temperatures beyond their melting points. They have been fully characterized and are readily soluble in a wide range of solvents. The conjugated rods are reversibly reduced in one‐electron transfer steps and cannot be oxidized below +1.23 V vs. Fc/Fc+. The effective conjugation length in PTAs was estimated from the electronic absorption (UV/Vis) data, and various evaluation methods yielded convergence of the optical properties in the range of 7 to 10 monomer units. The nonresonant second‐order molecular hyperpolarizability γ was measured in CHCl3 by means of the third harmonic generation (THG) at Δ = 1.907 μm. A plot of γ/n vs. n revealed a power law γ ≈ na for γ with a fitted exponent a = 2.5 ∓ 0.1. From the THG measurements, an effective conjugation length of about 10 monomer units was found, in surprisingly good agreement with the value obtained from UV/Vis spectroscopy data.
The Stable (Phosphino)(Silyl)Carbene As A Useful Building Block: Synthesis And Reactivity of 2‐Phosphorus‐Substituted 2H‐Azirines
Authors: Piquet Valérie , Baceiredo Antoine , Gornitzka Heinz , Dahan Françoise , Bertrand Guy 
Published: July 2007

Abstract[Bis(dicyclohexylamino)phosphino]trimethylsilylcarbene (1) reacts with benzonitrile leading to the corresponding 2‐phosphino‐2H‐azirine 3 in 85% yield. Treatment of 3 with trifluoro‐methanesulfonic acid, methyl trifluoro‐methanesulfonate, or elemental sulfur leads to the P‐hydrogeno‐2‐phosphonio‐,P‐methyl‐2‐phosphonio‐, or 2‐thioxo‐phosphoranyl‐2H‐azirine (4, 5, and 7) in 77, 87, and 91% yields, respectively. Irradiation of 3 gives rise to the 1,2λ5‐azaphosphete 8 (98% yield). Treatment of 3 with BF3·OEt2, BH3·SMe2, Lawesson's reagent, or methyl isothiocyanate gives heterocycles 9 (90% yield), 10 (76% yield), 12 (83% yield), or 13 (80% yield), while under the same experimental conditions, heterocycle 8 reacts with the same reagents to give 9 (82% yield), 11 (83% yield), 12 (86% yield), and 15 (56% yield), respectively. Thermolysis of the P‐hydrogeno‐2‐phosphonio‐2H‐azirine 4 at 55°C leads to the cationic, four‐membered heterocycle 17 (96% yield), while photolysis of the P‐methylazirine analogue 5 in the presence of dimethyl acetylenedicarboxylate affords pyrrole 19 (64% yield). Irradiation of the thiox‐ophosphoranyl azirine 7 gives the 1,3,5λ5‐thiazaphosphole 20 in 79% yield. The influence of the coordination state of phosphorus on the reactivity of 2‐phosphorus‐substituted 2H‐azirines is studied.
Aggregation, Reaggregation and Degradation of a Trifunctional Thallium(I) Amide Induced by Weak TlI ⃛ TlI Attraction
Authors: Hellmann Konrad W. , Gade Lutz H. , Fleischer Roland , Kottke Thomas 
Published: July 2007

AbstractMetal exchange of the solvated tripodal lithium amide [H3CC{CH2N(Li‐solv)SiMe3}3] (1, solv = ether solvent) with thallium(I) chloride leads to the previously reported pentametallated dimeric thallium amide [{H3CC(CH2NSiMe3)3}2(H)Tl5] (2) in high yield. That the redox‐induced partial demetallation of the amide presumably occurs at an intermediate stage of the metal exchange is inferred from the isolation and structural characterization of the mixed Tl‐Li amide [H3CC{CH3N(Tl) SiMe3}3][H3CC{CH2NSiMe3}3(H)(Tl)(Li‐thf)]·(toluene) (3), which has a crystal structure closely related to that of 2. In both cases the central structural motif, defined by weakly attractive Tl ⃛ Tl contacts, is a tetrahedral metal array in which a triangular thallium triamide unit is capped by an exposed Tl atom of a second building block. Compound 3 may be converted to 2 by metal exchange with TlCl. The two supramolecular components of 2 reaggregate upon recrystallization in a nonpolar solvent such as pentane to yield the dimeric aggregate of the fully metallated thallium amide [H3CC{CH2N(Tl)‐SiMe3}3]2 (4). An X‐ray crystallographic study of 4 established the existence of dimeric aggregation through Tl ⃛ Tl interactions leading to a more open dimeric form than 2 and 3, which is interpreted as being due to a structural mismatch of the building blocks. Compound 4 may be thermally degraded by prolonged stirring in toluene at ambient temperature to yield the previously reported mixed‐valence TlITlII amide [H3CC(CH2NSiMe3)3Tl2] (5).
Structure and Properties of Ba6Ni25S27
Authors: Gelabert M. C. , Ho M. H. , Malik A.‐S. , Disalvo F. J. , Deniard P. , Brec R. 
Published: July 2007

AbstractBa6Ni25S27, synthesized by solid‐state reaction of BaS, NiS, and Ni at 675°C, is cubic (Pm3m, a = 10.057(1) Å). The structure was refined by using powder X‐ray diffraction and Rietveld methods with Rp = 6.28%, Rwp = 8.13%, χ2 = 3.120. The structure, isotypic with Ba6Co25S27, consists of an extended network of Ni8S14 pseudo‐cube clusters, NiS6 octahedra, and Ba6S octahedra. Extended Hückel calculations of this compound indicate the band structure near the Fermi level to be composed mostly of d‐character orbitals of tetrahedral Ni, and reveal a peak in the density of states slightly below the Fermi level. The temperature dependence of the electrical resistivity exhibits a local maximum with thermal hysteresis at around 230 K. Above and below this transition, the slope of the resistivity is positive, with a room‐temperature resistivity (ρ = 0.23 mωcm) in the range for that of a poor metal conductor. Magnetic susceptibility measurements from 4 to 900 K indicate a sharp change in slope at around 225 K, with a steadily increasing susceptibility up to 900 K. The susceptibility below 225 K suggests Pauli paramagnetic behavior. Low‐temperature powder X‐ray diffraction and subsequent structure refinement shows that the lattice parameter, a, undergoes a slight change in slope at temperatures of around 235 K.
The Role of Fluorine in the Stereoselective Tandem Aza‐Michael Addition to Acrylamide Acceptors: An Experimental and Theoretical Mechanistic Study
Authors: Fustero Santos , Chiva Gema , Piera Julio , Volonterio Alessandro , Zanda Matteo , González Javier , Ramallal Antonio Morán 
Published: July 2007

AbstractAza‐Michael additions of α‐amino esters to fluorinated acceptors take place in a highly stereoselective manner, to give partially modified Ψ[NHCH2]retropeptides incorporating a hydrolytically stable trifluoroalanine mimic. The reaction mechanism has been investigated experimentally and theoretically, in order to explain the effect of the trifluoromethyl group on the reactivity and the origins of the experimentally observed stereocontrol. The reaction is a two‐step process, involving a tandem aza‐Michael addition followed by a stereoselective hydrogen transfer. Both steps are base‐catalyzed. The high level of stereocontrol is the result of a combination of electrostatic interactions and steric effects.
Improved glioblastoma treatment with Ad5/35 fiber chimeric conditionally replicating adenoviruses
Authors: Hoffmann Dennis , Meyer Bernhard , Wildner Oliver 
Published: July 2007

AbstractAdenovirus type 5 (Ad5)‐based vectors have been used in clinical trials for glioblastoma treatment, but the capacity of Ad5 to infect human glioma cells was questioned. Seeking to improve the adenovirus transduction, we tested four Ad5‐based vectors differing only in their fiber gene on permanent and short‐term cultures of glioblastoma cells. A wild‐type fiber Ad5 vector (Ad5.Luc) was compared to an RGD integrin‐binding motif‐containing fiber adenovirus (AdlucRGD) and the two fiber chimeras Ad5/3 and Ad5/35, with vector binding redirected to the Ad3 or Ad35 receptor, respectively. Compared to Ad5, the transduction of the tested short‐term glioblastoma cultures with the vector Ad5/35.Luc, AdlucRGD and Ad5/3.Luc was enhanced by ∼72%, ∼13% and ∼2%, respectively. To limit adenovirus spread, we aimed to develop conditionally replicative Ad5/35 vectors by targeting the expression of the essential E1 and E4 genes; in addition, some vectors had the E1Δ24 deletion. We analyzed eleven promoters for their activity in glioblastoma cells and determined the specificity of eight replicative adenovirus vectors in vitro. We evaluated the most promising vectors with E1/E4 under the control of the GFAP/Ki67 or E2F‐1/COX‐2 promoters, and the native Ad5 or the chimeric Ad5/35 fiber for their antineoplastic activity in a subcutaneous and intracranial glioblastoma xenograft model. Animals treated with the Ad5/35‐based vectors showed significantly smaller tumors and longer survival than those treated with the homologous Ad5 vectors; no significant toxicity was observed in the intracranial model. Our data suggest that Ad5/35‐based vectors are promising tools for glioblastoma treatment. Copyright © 2007 John Wiley & Sons, Ltd.
Offender and crime characteristics of female serial arsonists in Japan
Authors: Wachi Taeko , Watanabe Kazumi , Yokota Kaeko , Suzuki Mamoru , Hoshino Maki , Sato Atsushi , Fujita Goro 
Published: July 2007

AbstractThis study of Japanese female serial arsonists examined their crimes and background characteristics. The data were a sample from the national police register containing arson cases resulting in charges in Japan between 1982 and 2005. Serial arsonists were 6% of the arson offenders and 12% of these were female, resulting in 83 female serial arsonist data sets. The mean age was 37.6 years and 43% were unemployed. Nearly half were married. Only 28% had a documented history of mental problems and 22% had a prior arrest, usually for theft (19%). Female serial arsonists are characterised by going to a place near their home with a lighter and setting fire directly to combustible materials. Non‐metric multidimensional scaling was used to analyse 33 variables related to the offences. The arsons could be differentiated in terms of either expressive or instrumental sources of action. Expressive arsons were opportunistic and impulsive acts, motivated by emotional distress. The fires were mostly set close to home. Expressive arsons were characteristic of 66% of the females. Instrumental arsons were often motivated by revenge and involved planned and goal‐directed behaviours. They were committed by 13% of the females. Instrumental arsonists tended to travel further from home. Copyright © 2007 John Wiley & Sons, Ltd.
Inter‐ and intramolecular hetero Diels‐Alder reactions, 51. Intermolecular hetero Diels‐Alder reactions of enamino ketones. Effect of high pressure on the kinetics and diastereoselectivity
Authors: Tietze Lutz F. , Hübsch Thomas , Ott Christian , Kuchta Gabriele , Buback Michael 
Published: July 2007

AbstractThe hetero Diels‐Alder reaction of the enamino ketones 1b and 1c with ethyl vinyl ether (2) in dichloromethane to give the dihydropyrans 3b/4b and 3c/4c is studied at high pressure up to 5 kbar. The kinetics is measured by on‐line FT‐IR spectroscopy up to 3 kbar. The cycloadditions show a relatively high pressure‐dependent increase in diastereoselectivity in favor of the trans adducts 4b and 4c, respectively. The activation volumes at atmospheric pressure, ΔV, are determined to be −(43.3 ± 2.1) and −(43.9 ± 2.9) cm3 mol−1 for the reactions of 1b and 1c at 100°C in dichloromethane solution. The activation enthalpies, ΔH≠ for the two cycloadditions at 1500 bar are (64.4 ± 0.4) kJ mol−1 and (64.0 ± 0.6) kJ mol−1. The ΔΔV values are (3.8 ± 0.3) and (4.6 ± 0.3) cm3 mol−1 and the ΔΔH≠ values (1.5 ± 0.2) and (2.1 ± 0.3) kJ mol−1, respectively.
Substituenteneffekte auf die CC‐Bindungsstärke, 16. Thermische Stabilität und Bildungsenthalpie von β‐Dicarbonylverbindungen. — Stabilisierung von α,α′‐Diketoalkyl‐Radikalen
Authors: Nölke Margot , Verevkin Sergej P. , Beckhaus Hans‐Dieter , Rüchardt Christoph 
Published: July 2007

Substituent Effects on the CC Bond Strength, 16. — Thermal Stability and Enthalpies of Formation of β‐Dicarbonyl Compounds. — Stabilisation Enthalpies of α,α′‐Diketoalkyl RadicalsThe geminal interactions of the two carbonyl groups in seven β‐diketones of the type 8–9 and 11–13 were estimated from their enthalpies of formation, which were deduced from their heats of combustion and enthalpies of vaporization. The radical stabilisation enthalpies RSE of the α,α′‐diketoalkyl radicals 9–13 were obtained from the enthalpies of activation ΔH≠ of thermal CC bond cleavage of eight model compounds of the type 9–13 by their comparison with ΔH≠ of comparable hydrocarbons of similar strain. For non‐cyclic α,α′‐diacyl‐alkyl radicals and six‐membered cyclic ones RSE = 54.8 ± 1.3 kJ mol−1 was determined, which indicates an additive stabilisation by two carbonyl groups.
Strukturen und Moleküleigenschaften ladungsgestörter Moleküle, 54. Pyridinium‐tetraphenylcyclopentadienid‐Betain und die Einelektronen‐Oxidation zu seinem Radikalkation
Authors: Bock Hans , Nick Sabine , Näther Christian , Göbel Ilka , John Andreas , Kleine Markus 
Published: July 2007

Structures and Molecular Properties of Charge‐Perturbed Molecules, 54. — Pyridinium‐Tetraphenylcyclopentadienide Betaine and the Single‐Electron Oxidation to Its Radical CationThe single‐crystal structure of the dark‐blue pyridinium‐tetraphenylcyclopentadienide betaine shows the pyridine ring and the phenyl substituents twisted between 37 and 55°, indicating reduced π interactions between cos2 ω = 0.6 and 0.4. According to AM1 calculations based on the structure coordinates, the total charges of the pyridinium cation acceptor and the cyclopentadienyl anion donor amount to +0.62 and −0.53. This pronounced betaine zwitterionic character causes a 0.5 eV (!) bathochromic shift from 22000 cm−1 in aqueous to 18000 cm−1 in n‐heptane solution, which can be correlated with the respective ET solvent parameters. Cyclovoltammetry in H2CCl2/0.1 M R4N⊕ClO yields an irreversible reduction potential at −1.5 V and two oxidation potentials at +0.36 and +1.28 V, of which the lower one is reversible. With F3CCOO⊖Ag⊕, therefore, a radical cation can be generated and is characterized by ESR/ENDOR spectra. The coupling constants are satisfactorily reproduced by McLachlan calculations, which also suggest that most of the spin population should be localized within the five‐membered ring.
Kleine Ringe, 85. Versuche zur Darstellung von Alkyltri‐tert‐butyltetrahedranen auf dem Cyclopentadienon‐Weg; Synthese der Cyclopentadienone
Authors: Maier Günther , Franz Lothar Hermann 
Published: July 2007

Small Rings, 85. — Attempts to Synthesize Alkyltri‐tert‐butyltetrahedranes by the Cyclopentadienone Route; Synthesis of the CyclopentadienonesStarting from 2‐bromotri‐tert‐butylcyclopentadienone (1) a series of highly substituted cyclopentadienones has been prepared, hoping that they might be suitable candidates for the synthesis of a variety of tetrahedranes with different sterically demanding substituents.
Kleine Ringe, 89. Eine alternative Synthese von Tetra‐tert‐butyltetrahedran
Authors: Maier Günther , Fleischer Frank 
Published: July 2007

Small Rings, 89. – An Alternative Synthesis of Tetra‐tert‐butyltetrahedraneCyclopropenyldiazomethane 3 is an ideal precursor for tetra‐tert‐butyltetrahedrane (6). Both, photochemical and thermal decomposition of 3 lead to cyclobutadiene 7, which can be photoisomerized to tetrahedrane 6. Tetra‐tert‐butyltetrahedrane (6) is also formed directly by a cheletropic cycloaddition of the carbenic center to the cyclopropene double bond in carbene 4. This is the first example for the synthesis of a tetrahedrane, which does not occur via the corresponding cyclobutadiene. The formation of pyridazine 10 dominates the thermolysis of 3. Azete 12 is obtained both by photolysis as well as by thermolysis of Dewar‐pyridazine 11, the irradiation product of 10.
Synthesis of fluorenylidene‐ and 9‐alkylidene‐3,6‐dimethyl‐4,5‐diazafluorene compounds from 2,2′‐biarene‐3,3′‐diyl bis(triflate) by a palladium‐catalyzed domino process
Authors: König Burkhard , Bubenitschek Peter , Jones Peter G. 
Published: July 2007

AbstractA convenient synthesis of the fluorenylidene and the 4,5‐diazafluorenylidene moiety is described. The palladium‐catalyzed coupling of 6,6′‐dimethyl‐2,2′‐bipyrdine‐3,3′‐diyl bis(triflate) (2) with phenylacetylene leads to the 4,5‐diazafluorenylidene compound 4 as the major reaction product by an intramolecular cyclization. Under the same conditions biphenyl‐2,2′‐diyl bis(triflate) (6) gives the threefold coupling product 7. The connectivity of 4 and 7 is confirmed by crystal structure analysis.
α,ω‐Dialkyl‐substituted polyenes by palladium‐catalyzed coupling reactions of vinyltin compounds with vinyl halides
Authors: Kiehl Alfried , Eberhardt Anke , Müllen Klaus 
Published: July 2007

Abstractα,ω‐Dialkyl‐substituted linear polyenes are synthesized in good yields by the palladium‐catalyzed coupling reaction of trialkyltin‐ and iodo‐substituted olefinic precursors. Central building blocks are the distannylated butadiene 8 and vinyl iodide 3. Our synthetic strategy was successfully applied to the preparation of the tert‐butyl polyenes 13, 14, and 15 as well as polyenes 25 and 26 with longer α,ω‐dialkyl chains.
Sterically congested molecules, 14. Imine protonation in toluene solution: A problem akin to the N‐protonation in rhodopsin
Authors: Knorr Rudolf , Ferchland Kathrin 
Published: July 2007

AbstractThe protonation state of N‐(1,1,3,3‐tetramethyl‐2‐indanylidene)methylamine (5/6) is assessed on the basis of fully assigned 1H‐ and 13C‐NMR spectra in [D8]toluene and in CDCl3. In either solvent the basicity of 5 remains intermediate between those of pyridine (weaker) and triethylamine (stronger). Nearly complete proton transfer to 5 in toluene occurs with trifluoroacetic and dichloroacetic acids, whereas partial protonation is achieved by chloroacetic acid or acetic acid and even by biphenyl‐2,2′‐diol (7). As a possible model for imine protonation in the hydrophobic region of proteins like the rhodopsins, the sterically shielded iminium cation 6 (or 2) does not require solvation by a polar solvent; rather it can be stabilized in toluene solution by a counteranion whose proton affinity is diminished by an assisting hydrogen bond.
Sterically congested molecules, 15. Estimation of the ion‐pair NH‐acidity constant of the imino function
Authors: Knorr Rudolf , Ferchland Kathrin 
Published: July 2007

AbstractThe lithium imide 3 is slightly more basic than lithium bis(tri‐methylsilyl)amide (5c) in THF solution. Based on a reported pKa value for hexamethyldisilazane (4c) and assuming the simplest form of ion‐pair equilibration in eq. 1, the apparent pKa = 26.5 was determined for the imine 6.
Ein einfacher Weg zu 3′‐Desoxy‐α‐L‐ und 3′‐Desoxy‐β‐D‐apionucleosiden
Authors: Hammerschmidt Friedrich , Öhler Elisabeth , Polsterer Johann‐Peter , Zbiral Erich , Balzarini Jan , Declercq Erik 
Published: July 2007

A Convenient Route to 3′‐Deoxy‐α‐L‐ and 3′‐Deoxy‐β‐D‐apionucleosidesThe cyclic thionocarbonate 3, easily available in three steps from 3′‐O‐benzoyl‐2,3‐O‐isopropylidene‐D‐apio‐β‐D‐furanose (1), is deoxygenated with n‐Bu3SnH to yield the 3′‐deoxy epimers 4 [methyl 3‐C‐(benzoyloxymethyl)‐3‐deoxy‐α‐L‐threo‐tetrofuranoside] and 6 [methyl 3‐C‐(benzoyloxymethyl)‐3‐deoxy‐β‐D‐erythro‐tetrofuranoside]. These are separated by chromatography and further converted to the 3′‐deoxy‐α‐L‐apionucleosides 11–13, and the 3′‐deoxy‐β‐D‐apionucleosides 17–19, respectively.