催化不对称反应新进展—不对称活化

介绍了催化不对称催化反应中的一个新概念一不对称活化(asymmetric activation)及其研究的最新进展。运用不对称活化策略,一个光学活性的或者甚至外消旋的催化剂可以被另一种手性活化剂(chiral activator)选择性地活化,从而催化反应生成非外消旋产物。该方法较不对称去活化(asymmetric deactivation)方法的优点是被活化的催化剂能够产生较使用光学纯催化剂更高对映体过量的产物。     

铜催化不对称烯丙基烷基化反应的研究进展

铜催化不对称烯丙基烷基化反应是一种重要的合成手性化合物的方法,综述了铜催化不对称烯丙基烷基化反应的最新研究进展,重点讨论了烯内基衍,生 物结构、手性配体结构及亲核试剂类型等因素对该类型反应的影响.     

手性金属络合物催化不对称Baeyer-Villiger反应

Baeyer-Villiger反应是有机化学基本反应之一,但是催化不对称Baeyer-Villiger反应的研究尚处于起步阶段。本文按手性配体的不同,评述了手性金属络合物催化不对称Baeyer-Villiger反应的研究,特别是由外消旋或前手性酮制备光学活性内酯的研究进展。     

手性磷酸催化的有机催化不对称反应

手性磷酸是近年来发展起来的一类新型高效、高对映选择性的Brønsted酸类有机催化剂, 已成功应用于催化不对称Mannich反应、还原胺化反应、Pictet-Spengler反应、aza-Diels-Alder反应和aza-Ene反应等许多重要的有机合成反应. 手性磷酸催化剂分子内同时含有Lewis碱性位点和Brønsted酸性位点, 可同时活化亲电与亲核底物. 作为一种新型双功能有机催化剂, 手性磷酸具有较高的催化活性和对映选择性, 催化剂最低用量可达0.05 mol%. 对各类手性磷酸催化剂在有机催化不对称合成反应中的应用研究进展, 以及不对称诱导反应的机理、手性磷酸的分子结构及反应条件对其催化活性和不对称诱导活性的影响进行了评述.     

不对称催化环氧化反应

本文综述了不对称催化环氧化体系的研究进展。重点评述了Sharpless-Kat-suki不对称环氧化反应的特点、机理、新进展与应用,综合分析了由手性(salen)Mn(Ⅲ)催化剂对非功能化烯烃所创建的突出成果与应用前景。     

生物催化烯烃不对称环氧化反应

手性环氧化物在合成上具有重要的应用价值。近年来,制取这些手性合成物的合成方法取得了很大的发展。文章重点讨论了生物催化手性前体烯烃不对称合成光学活性环氧化合物的发展状况。     

手性高分子金属络合物催化的不对称有机反应研究进展

本文评述了近年来在手性高分子金属络合催化的不对称有机反应方面的研究进展。     

烯烃的有机催化不对称环氧化反应

介绍了用手性酮，手性亚胺盐为催化剂以及手性胺为催化剂前体的新型有机催化不对称环氧化反应。     

手性烯烃配体在不对称催化领域的最新进展

手性烯烃配体是一类具有重要应用前景的新型配体,自发展以来就引起化学家们的广泛关注.手性烯烃配体在一些反应中表现出比传统氮、磷、氧配体更高的活性和选择性,实现了一些使用其它类型配体不能实现的化学转化.为了增强手性烯烃配体与金属的配位能力,化学家们在其骨架上引入杂原子,发展得到混合型的烯烃配体,增加了配体的多样性,对进一步拓展手性烯烃配体的类型和应用具有非常重要的意义.目前关于手性烯烃配体已经有一些综述,本综述将着重介绍最近几年来发展的手性开链双烯配体、手性膦烯烃配体和手性硫烯烃配体及其在过渡金属催化的不对称反应领域的应用.     

催化不对称碳硼成键反应研究进展

从不对称催化的角度总结了近年来碳硼成键反应的研究进展,评述了这些反应各自的特点,并对其未来研究进行了展望.     

Recent advances towards catalytic asymmetric Conia-ene-type reactions

Conia-ene reactions,as a type of ene reactions,have not become a remarkable focus until the beginning of21~(st) century,when Lewis acids served as powerful catalysts and found an increasingly broad utilization in this field.Consequently,the catalytic Conia-ene reactions have gained great significance in synthetic chemistry due to their high efficiency and atom economy on the construction of valuable cyclic molecules.During the past two decades,the rapid development of transition-metal catalysis and organocatalysis has imposed a profound impact on the exploration of asymmetric Conia-ene reactions.As a result,several strategies have been developed and applied successfully.Organized on the basis of the catalytic system,this review comprehensively presents a summary of recent progress achieved in this emerging domain,aimed at highlighting the reactions' features,practicalities,and the mechanistic rationale is presented where possible.     

Recent developments in the catalytic asymmetric synthesis of alpha- and beta-amino acids

The stereoselective synthesis of amino acids is of great importance for the construction of optically active natural products and pharmaceuticals. Apart from enzymes, a broad repertoire of chiral reagents, auxiliaries, and catalysts can be used for the formation of amino acids. Asymmetric reactions using catalytic amounts of chiral molecules provide efficient methods for the generation of optically active proteinogenic and nonproteinogenic amino acids. This minireview collects recent work on catalytic asymmetric synthesis of alpha- and beta-amino acids.     

Recent advances in direct catalytic asymmetric transformations under proton-transfer conditions

Cooperative catalysis has proven to be a particularly powerful strategy for promoting stereoselective organic transformations under mild reaction conditions. The specific interactions between the catalyst components and substrates are precisely orchestrated to elicit high catalytic efficiency and excellent control of the stereochemical course. By harnessing the power of cooperativity, various sets of stereoselective reactions proceed under mild proton-transfer conditions with perfect atom economy. This Minireview summarizes our recent contributions to several C-N and C-C bond-forming reactions in this field and related transformations.     

抗体酶催化的不对称反应

本文综述了抗体酶催化的不对称反应, 并讨论了抗体酶的应用前景。     

Recent progress on direct catalytic asymmetric vinylogous reactions

Direct catalytic asymmetric vinylogous reaction serves as a powerful tool to introduce stereocenter(s) at the γ- or/and even more remote position(s) of the vinylogous products in an atom-economical and efficient way. A variety of direct catalytic asymmetric vinylogous reactions with broad substrate scope and mild reaction conditions has been developed. Both metal catalysis and organocatalysis contributed in this field and led to the vinylogous products in high stereoselectivity. These vinylogous reactions provided efficient pathways for the synthesis of highly functionalized optically pure compounds, especially these with potential biological activity and pharmacological activity. This digest paper mainly focuses on the most recent developments in this field, including both nucleophilic addition and nucleophilic substitution.     

醛不对称加成反应的进展

综述了近年来醛不对称加成反应的进展,包括加氘还原、与有机金属化合物加成、与有机硼化合物加成、与氰化物加成、与磷酸酯加成和aldol加成等反应。     

Recent advances in asymmetric phase-transfer catalysis

The use of chiral nonracemic onium salts and crown ethers as effective phase-transfer catalysts have been studied intensively primarily for enantioselective carbon-carbon or carbon-heteroatom bond-forming reactions under mild biphasic conditions. An essential issue for optimal asymmetric catalysis is the rational design of catalysts for targeted reaction, which allows generation of a well-defined chiral ion pair that reacts with electrophiles in a highly efficient and stereoselective manner. This concept, together with the synthetic versatility of phase-transfer catalysis, provides a reliable and general strategy for the practical asymmetric synthesis of highly valuable organic compounds.