共查询到20条相似文献,搜索用时 15 毫秒
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Yu‐Hua Deng Jin‐Quan Chen Dr. Long He Dr. Tai‐Ran Kang Prof. Quan‐Zhong Liu Prof. Shi‐Wei Luo Prof. Wei‐Chen Yuan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7143-7150
Highly enantioselective cross‐aldol reactions between acetaldehyde and activated acyclic ketones are reported for the first time. Various acyclic ketones, such as saturated and unsaturated keto esters, reacted with acetaldehyde in the presence of a chiral primary amine and a Brønsted acid to afford optically enriched tertiary alcohols in good yields and with excellent enantioselectivities. Trifluoromethyl ketones were tolerable under the reaction conditions, thereby affording the trifluoromethyl carbinol in good‐to‐excellent yields and enantioselectivities. Structural modification of the chiral amines from the same chiral source switched the stereoselectivity of the products. The utility of aldol chemistry was demonstrated in the brief synthesis of functionally enriched δ‐lactones. Theoretical calculations on the transition‐state structure indicated that the protonated tertiary amine could effectively activate the carbonyl group of a keto ester to promote the addition process through hydrogen‐bonding interaction and, simultaneously, provide an appropriate attacking pattern for the approach of the keto ester to the enamine, which is formed from acetaldehyde and the chiral catalyst, on a particular face, resulting in high enantioselectivity. 相似文献
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Marcus Frings Iuliana Atodiresei Dr. Jan Runsink Dr. Gerhard Raabe Prof. Dr. Carsten Bolm Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(7):1566-1569
In control : A new catalytic vinylogous Mukaiyama aldol reaction provides products with high diastereo‐ and enantioselectivities (up to 99 % de and ee; see scheme). The relative and absolute stereochemistry of a representative product was rigorously assigned by NMR and CD spectroscopies (measured and calculated), X‐ray diffraction, and quantum‐chemical calculations.
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Organocatalytic Atroposelective Aldol Condensation: Synthesis of Axially Chiral Biaryls by Arene Formation 下载免费PDF全文
Achim Link Dr. Christof Sparr 《Angewandte Chemie (International ed. in English)》2014,53(21):5458-5461
Axially chiral compounds are of significant importance in modern synthetic chemistry and particularly valuable in drug discovery and development. Nonetheless, current approaches for the preparation of pure atropisomers often prove tedious. We demonstrate here a synthetic method that efficiently transfers the stereochemical information of a secondary amine organocatalyst into the axial chirality of tri‐ortho‐substituted biaryls. An aromatic ring is formed during the dehydration step of the described aldol condensation cascade, leading to highly enantioenriched binaphthyl derivatives. The fundamental course of the reaction is related to the biosynthesis of aromatic polyketides. 相似文献
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Florian Livernaux Sidonie Laviéville Pascale Guiffrey Prof. Dr. Jean-Marc Campagne Dr. Eric Leclerc 《European journal of organic chemistry》2023,26(32):e202300467
The enantioselective addition of difluoroenoxysilanes to aromatic aldehydes, catalyzed by cationic palladium aqua complexes, has been described. The reaction is operationally simple, does not require anhydrous conditions and performs at room temperature. The palladium catalysts, previously discovered and reported by Sodeoka, are easily prepared in two steps from PdCl2(MeCN)2. The aldol compounds were obtained in good yields and with enantiomeric ratios up to 93 : 7, the reaction being more efficient using electron-rich aldehydes. 相似文献
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A new proline catalyst, namely (N′‐benzyl‐N′‐D‐prolyl)‐trans‐4‐hydroxy‐L‐proline hydrazide, has been prepared and proved to be a superior catalyst for the asymmetric aldol reaction of cyclohexanone and aromatic aldehydes, affording up to 98:2 dr and 98% ee. 相似文献
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本文研究了精氨酸在水中催化羟醛缩合反应,结果表明:精氨酸在水相中可作为一种高效的有机小分子催化剂,催化缺电子芳香醛与酮间的反应,催化剂精氨酸可以回收重复使用10次,催化活性基本不变。 相似文献
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Magnus Rueping Prof. Dr. Alexander Kuenkel Dipl.‐Chem. Francisco Tato Dr. Jan W. Bats Dr. 《Angewandte Chemie (International ed. in English)》2009,48(20):3699-3702
C′mon 1,2‐dione : A new diastereo‐ and enantioselective Lewis base catalyzed domino Michael/aldol reaction converts α,β‐unsaturated aldehydes and 1,2‐diones into chiral bicyclo[3.2.1]octane‐6‐carbaldehydes. The products are produced in good to excellent enantioselectivities (90–98 % ee) and can be transformed into bicyclic diols and triols. Additionally, a retro‐aldol cyclization provides access to valuable tetrahydrochromenones (see scheme).
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Pinches like a crab : The utilization of guanidines as catalysts has been growing at a steady pace. They possess high pKa values and activate through dual hydrogen‐bonding modes of activation. This Focus Review highlights the development of chiral guanidine catalysts in asymmetric organic transformations.
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Over the past decade, organocatalysis has emerged as a powerful tool for stereoselective carbon-carbon bond formation under exceptionally mild conditions. The organocatalytic versions of a large number of traditional synthetic transformations are now well established and the quest for new applications of the basic concepts of organocatalysis continues. This review addresses the emergent interest in the organocatalytic vinylogous aldol reaction. While noteworthy progress has been made in this area, significant challenges lie ahead. 相似文献
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The enantioselective allylic amination of Morita‐Baylis‐Hillman acetates catalyzed by chiral cyclohexane‐based thiourea‐phosphine catalysts was investigated. In the presence of 20 mol% rosin‐derived thiourea‐phosphine 3j , the chiral amines were obtained in up to 88% yield and up to 85% ee. 相似文献
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研究实现了多功能手性膦催化的3-芳酰基丙烯酸酯和烯酮的不对称分子间Rauhut-Currier反应,为多羰基手性化合物的构建提供了一种新方法.在使用(S,RS)-X8作为催化剂和甲苯作为溶剂的条件下,一系列含有不同取代基团的3-芳酰基丙烯酸酯和烯酮均可顺利地发生不对称Rauhut-Currier反应,从而高产率且高对映选择性地生成相应的产物.对照实验表明多功能手性膦催化剂中的N-H键对反应的对映选择性的控制起到了至关重要的作用;膦谱监测实验结果表明手性膦催化剂对烯酮的Michael加成是该反应的启动步骤. 相似文献