共查询到20条相似文献,搜索用时 15 毫秒
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《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(2):568-575
The reaction of ester‐stabilized sulfonium ylides with cyclopentenone to give (+)‐ 5 ((1S,5R,6S)‐ethyl 2‐oxobicyclo[3.1.0]hexane‐6‐carboxylate), an important precursor to the pharmacologically important compound (+)‐LY354740, has been studied using chiral sulfides operating in both catalytic (sulfide, Cu(acac)2, ethyl diazoacetate, 60 °C) and stoichiometric modes (sulfonium salt, base, room temperature). It was found that the reaction conditions employed had a major influence over both diastereo‐ and enantioselectivity. Under catalytic conditions, good enantioselectivity with low diastereoselectivity was observed, but under stoichiometric conditions low enantioselectivity with high diastereoselectivity was observed. When the stoichiometric reactions were conducted at high dilution, diastereoselectivity was reduced. This indicated that base‐mediated betaine equilibration was occurring (which is slow relative to ring closure at high dilution). Based on this model, conditions for achieving high enantioselectivity were established as follows: use of a preformed ylide, absence of base, hindered ester (to reduce ylide‐mediated betaine equilibration), and low concentration. Under these conditions high enantioselectivity (95 % ee) was achieved, albeit with low diastereocontrol. Our model for selectivity has been applied to other sulfonium ylide mediated cyclopropanation reactions and successfully accounts for the diastereoselectivity observed in all such reported reactions to date. 相似文献
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Chiral oxathianes were designed, synthesized, and successfully used for asymmetric sulfur ylide mediated epoxidation. A considerable emphasis has been placed upon the design of sulfides with suitable architecture in a small number of steps (three or four). The use of (4aR,6S,8aR)‐6‐isopropenyl‐8a‐methyloctahydro‐1,4‐benzoxathiane in asymmetric epoxidation resulted in good diastereo‐ and enantioselectivity in the formation of stilbene oxide, and (2S,6S)‐2‐allyl‐2,3,3,6‐tetramethyl‐1,4‐oxathiane produced even better results. Moderate to good diastereoselectivities with essentially complete enantioselectivities were observed in the formation of alkyl–aryl‐, vinyl–aryl‐, and propargyl–aryl‐substituted epoxides. The selectivities were rationalized and supported by density functional theory calculations. 相似文献
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Guo‐Shu Chen Shu‐Jie Chen Jian Luo Xiang‐Yu Mao Albert Sun‐Chi Chan Raymond Wai‐Yin Sun Yun‐Lin Liu 《Angewandte Chemie (International ed. in English)》2020,59(2):614-621
Tandem reactions of Pd‐catalyzed cross‐coupling of 3‐(2‐isocyanoethyl)indoles with diazoacetates and subsequent spirocyclization/Mannich‐type reaction have been developed to assemble polycyclic spiroindoline skeletons. Formation of spiroindolenines has been proven as the crucial step for the following Mannich‐type cyclization reaction. Accordingly, a novel approach on chiral phosphoric acid catalyzed Mannich‐type cyclization toward the formation of diastereomerically and enantiomerically enriched pentacyclic spiroindolines has been established. Moreover, the products of the reaction are versatile building blocks in synthetic chemistry, as demonstrated by the synthesis of the key framework of aspidosperma and kopsia alkaloids. 相似文献
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Iain Coldham Prof. Sophie Raimbault Dr. David T. E. Whittaker Dr. Praful T. Chovatia Dr. Daniele Leonori Jignesh J. Patel Dr. Nadeem S. Sheikh Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(13):4082-4090
Proton abstraction of N‐tert‐butoxycarbonyl‐piperidine (N‐Boc‐piperidine) with sBuLi and TMEDA provides a racemic organolithium that can be resolved using a chiral ligand. The enantiomeric organolithiums can interconvert so that a dynamic resolution occurs. Two mechanisms for promoting enantioselectivity in the products are possible. Slow addition of an electrophile such as trimethylsilyl chloride allows dynamic resolution under kinetic control (DKR). This process occurs with high enantioselectivity and is successful by catalysis with substoichiometric chiral ligand (catalytic dynamic kinetic resolution). Alternatively, the two enantiomers of this organolithium can be resolved under thermodynamic control with good enantioselectivity (dynamic thermodynamic resolution, DTR). The best ligands found are based on chiral diamino‐alkoxides. Using DTR, a variety of electrophiles can be used to provide an asymmetric synthesis of enantiomerically enriched 2‐substituted piperidines, including (after Boc deprotection) the alkaloid (+)‐β‐conhydrine. The chemistry was extended, albeit with lower yields, to the corresponding 2‐substituted seven‐membered azepine ring derivatives. 相似文献
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5‐(Alkynyl)dibenzothiophenium Triflates: Sulfur‐Based Reagents for Electrophilic Alkynylation 下载免费PDF全文
M. Sc. Bernd Waldecker Finn Kraft Dr. Christopher Golz Prof. Dr. Manuel Alcarazo 《Angewandte Chemie (International ed. in English)》2018,57(38):12538-12542
The synthesis of a series of 5‐(alkynyl) dibenzothiophenium triflates, prepared from dibenzo[b,d]thiophene 5‐oxide and the corresponding trimethylsilyl‐substituted alkynes is reported. Their structures were determined by X‐ray crystallography, and their reactivities as electrophilic alkynylation reagents evaluated. Their broad substrate scope and functional‐group tolerance illustrate their potential to become an alternative to the broadly used EBX reagents. Isotope labeling studies reveal that alkynyldibenzothiophenium salts may undergo attack by nucleophiles at either the α‐ or β‐carbon atom depending on the nature of their substitution pattern. Subsequent elimination of the dibenzothiophene unit and 1,2‐migration of one of the groups (in case of β‐attack) affords the desired alkynes. 相似文献
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Daniel Glynn Jonathan Shannon Dr. Simon Woodward Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(3):1053-1060
A practical asymmetric 1,2‐addition of functionalised arylzinc halides to aromatic and aliphatic aldehydes is described by the use of aminoalcohol catalysis in the presence of AlMe3. The process is simple to carry out, uses only commercially available reagents/ligands and provides moderate to good (80–96 % ee) enantioselectivities for a wide range of substrates. Either commercial ArZnX reagents or those prepared in situ from low cost aryl bromides can be used. In the latter case electrophilic functional groups are tolerated (CO2Et, CN). The reaction relies on rapid exchange between ArZnX and AlMe3 to generate mixed organometallic species that lead to the formation of a key intermediate that is distinctly different from the classic “anti” transition states of Noyori. NMR monitoring and related experiments have been used to probe the validity of the proposed selective transition state. 相似文献
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[CpRu]‐Catalyzed Carbene Insertions into Epoxides: 1,4‐Dioxene Synthesis through SN1‐Like Chemistry with Retention of Configuration 下载免费PDF全文
Dr. Thierry Achard Cecilia Tortoreto Dr. Amalia I. Poblador‐Bahamonde Dr. Laure Guénée Prof. Thomas Bürgi Prof. Jérôme Lacour 《Angewandte Chemie (International ed. in English)》2014,53(24):6140-6144
Rather than lead to the usual deoxygenation pathway, metal carbenes derived from α‐diazo‐β‐ketoesters undergo three‐atom insertions into epoxides using a combination of 1,10‐phenanthroline and [CpRu(CH3CN)3][BArF] as the catalyst. Original 1,4‐dioxene motifs are obtained as single regio‐ and stereoisomers. A perfect syn stereochemistry (retention, e.r. up to 97:3) is observed for the ring opening, which behaves as an SN1‐like transformation. 相似文献
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Direct Synthesis of Chiral Allenoates from the Asymmetric CH Insertion of α‐Diazoesters into Terminal Alkynes 下载免费PDF全文
Yu Tang Quangang Chen Prof. Dr. Xiaohua Liu Gang Wang Dr. Lili Lin Prof. Dr. Xiaoming Feng 《Angewandte Chemie (International ed. in English)》2015,54(33):9512-9516
The asymmetric C? H insertion of α‐diazoesters into 1‐alkynes was achieved using chiral cationic guanidinium salts and copper(I) complexes. Optically active 2,4‐disubstituted allenoates were generated under mild reaction conditions from various α‐diazoesters and 1‐alkynes in high yield (up to 99 %) and enantioselectivity (up to 97:3 e.r.). Control experiments excluded the possibility of an asymmetric isomerization of alkynoates. 相似文献
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