烯烃的催化不对称氨羟基化反应

烯烃的催化不对称氨羟基化反应是Ｓｈａｒｐｌｅｓｓ继手性钛络合物催化的烯丙醇的不对称环氧化反应和烯烃的催化不对称双羟基化反应这后发现的又一极为重要的催化不对称反应。本文对这一新反应作一综述。     

Salen Mn(Ⅲ)催化的双键不对称环氧化研究进展

SalenMn(Ⅲ)络合物是催化双键不对称环氧化的一类很重要的催化剂。本文综述了salenMn(Ⅲ)络合物的设计、其催化双键不对称环氧化的反应和机理以及轴向配体、电子效应等对反应的影响等方面的研究进展,并总结了这一催化体系在顺式烯烃、环内烯烃、三取代烯烃的不对称环氧化反应和反式环氧化物的生成中的应用及其优点。     

手性铁催化体系在不对称催化中的应用研究

本文介绍了手性铁催化体系在酮及亚胺的不对称还原、烯烃及硫醚的不对称氧化、不对称环加成、不对称环丙烷化以及不对称Friedel-Crafts烷基化等反应中的应用.     

光学活性沙丁胺醇的不对称合成研究进展

综述了不对称反应合成光学活性沙丁胺醇的研究进展。其中包括手性辅基诱导、不对称硼氢化、不对称催化氢化、不对称转移氢化、不对称双羟基化反应、酶催化的不对称氰醇化反应等。     

手性催化剂与不对称反应

不对称催化合成是有机合成中越来越重要的一个分支。本文综述了几类不对称反应的进展。其中包括氢化、环氧化、环丙烷化、烯丙基烷基化、Diels—Alder反应等。并讨论了其中某些反应的机理以及催化剂结构与性能的关系。     

手性氨基酚配体及其衍生物在不对称催化中的应用

综述了手性氨基酚配体及其衍生物的研究进展, 着重介绍其在不对称催化烷基化、烯基化、Michael加成、aldol反应及环丙化等反应中的应用.     

手性Salen Mn(Ⅲ)配合物催化NaOCl不对称环氧化苯乙烯反应

手性Salen Mn(Ⅲ)配合物催化NaOCl不对称环氧化苯乙烯反应;不对称环氧化;Salen Mn(Ⅲ)配合物;苯乙烯;NaOCl     

手性pybox-金属络合物及其在不对称催化反应中的应用

具有C2对称性的双噁唑啉型吡啶(pybox)是一类有效的手性配体,能与许多金属离子配位,其手性催化性能已得到越来越多的关注。本文综述了手性配体pybox和pybox-金属络合物的合成方法,特别是近年来pybox-金属络合物在不对称催化反应如不对称环丙烷化反应、不对称Diels-Alder反应、1,3-偶极环加成反应、不对称aldol反应等中应用的最新进展。     

不对称有机催化Michael加成/半缩醛胺化/酰亚胺正离子环化串联反应研究进展

随着近十多年来不对称有机小分子催化的发展,以这类催化为基础的串联反应也取得了很大的进展.综述了近几年来不对称有机催化Michael加成/半缩醛胺化/酰亚胺正离子环化串联反应构建手性氮杂多环结构的研究进展,介绍了国内外多个课题组对这一类反应的研究结果以及该类反应在生物碱合成中的应用.     

用原位变温19F NMR研究三氟甲磺酸根在苯乙烯不对称环丙烷化反应中的作用

近几年来,对含有弱配位阴离子如OTf^-（三氟甲磺酸根）,BF4^-,PF6^-和AsF6^-等有机金属化合物的研究逐渐引起人们的关注,这些弱配位阴离子具有较高的反庆活性,是很好的离去基团,并且可在非常温和的反应条件下被其它配体取代,所以它们是金属有机合成中的一种非常有用的合成子,最近,这种具有弱配位能力的阴离子在不对称催化中的也取得了很好的结果,在不对称催化体系中引入弱配位阴离子可以极大地改善催化体系的活性,我们在研究手性胺、膦配体在不对称环丙烷化反应中的应用时发现三氟甲磺酸根也表现出这种性质,当在手性胺、膦钌配合物催化体系中加入三氟甲磺酸银后,不对称环丙烷化反应的产率有大幅度提高,但是人们对弱配位阴离子在催化反应中的作用机理的研究还不太多,本文利用原位变温^19F NMR技术研究了三氟甲磺酸根在手性胺、膦钌配合物催化的苯乙烯不对称环丙烷化反应中的作用。     

离子液体/超临界二氧化碳两相体系在有机合成中的应用

介绍了近年来在离子液体/超临界二氧化碳两相体系中进行有机合成的最新进展, 包括烯烃氢甲酰化反应、酶催化反应、二氧化碳和环氧化物的环加成反应、烯烃环氧化反应、烯烃不对称二羟化反应、氢化反应、Heck反应、醇氧化反应、烯烃氢乙烯化反应、烯烃二聚反应等.     

Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes

Terminal alkenes are readily available functional groups which appear in α‐olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1‐alkenes is high enough to be useful for asymmetric synthesis.     

Azaarene cis-dihydrodiol-derived 2,2'-bipyridine ligands for asymmetric allylic oxidation and cyclopropanation

Biphenyl dioxygenase-catalysed cis-dihydroxylation of 2-chloroquinoline, 2-chloro-3-methylquinoline and 2-chloro-6-phenylpyridine substrates yielded the corresponding enantiopure cis-dihydrodiols; enantiopure 2,2'-bipyridines, synthesised in four steps from 2-chloroquinoline, proved to be efficient chiral ligands in catalytic asymmetric allylic oxidation and cyclopropanation reactions of alkenes.     

Synthesis of a new chiral nonracemic C(2)-symmetric 2,2'-bipyridyl ligand and its application in copper(I)-catalyzed enantioselective cyclopropanation reactions

An efficient synthesis of a low molecular weight, chiral nonracemic and C(2)-symmetric bipyridyl ligand is reported. The ligand was prepared using a catalytic asymmetric dihydroxylation reaction of a pyrindine as a key step. The ligand was evaluated in the asymmetric copper(I)-catalyzed cyclopropanation reactions of a series of alkenes and diazoesters. Very high diastereoselectivities and enantioselectivities were observed (>95:5 dr and up to 99% ee). These are the highest reported stereoselectivities for a chiral bipyridyl ligand. [structure: see text]     

Rhodium-catalyzed enantioselective diboration of simple alkenes

Enantioselective catalytic reactions that operate directly on inexpensive unactivated alkenes are extraordinarily useful for the preparation of chiral organic building blocks and new materials. While a number of such processes have been developed, our ability to meet the intensifying demand for inexpensive stereochemically complex materials will require a significant expansion of practical catalytic asymmetric reaction methodology. In this regard, the rhodium-catalyzed enantioselective diboration reaction has been developed in order to address a number of extant problems in catalytic alkene transformation simultaneously. This process provides an enantiomerically enriched reactive dimetalated intermediate which can be converted to a variety of difunctional reaction products.     

New Catalytic Approaches towards the Enantioselective Halogenation of Alkenes

The addition of electrophilic reagents to the carbon–carbon double bond is one of the most fundamental reactions in organic chemistry. Halogen electrophiles constitute probably the most important class of electrophiles and have been widely used to induce electrophilic addition reactions to alkenes like halolactonizations or dihalogenations. Despite their long history and high importance, catalytic, asymmetric variants of these reactions have been underdeveloped until very recently. During the last two years this has changed and many novel approaches have been reported. This review aims to cover these new developments through discussing the common themes as well as the suggested mechanistic scenarios.     

Sulfinate and Carbene Co‐catalyzed Rauhut–Currier Reaction for Enantioselective Access to Azepino[1,2‐a]indoles

A carbene and sulfinate co‐catalyzed intermolecular Rauhut–Currier reaction between enals and nitrovinyl indoles is disclosed. The carbene catalyst activates the enal and the sulfinate co‐catalyst activates the nitrovinyl indole. Both activation processes are realized via the formation of covalent bonds between the catalysts and substrates to generate catalyst‐bound intermediates. The dual catalytic reaction affords azepino[1,2‐a]indole products with excellent stereoselectivity. Our study demonstrates the unique involvement of sulfinate as an effective nucleophilic catalyst in activating electron‐deficient alkenes for asymmetric reactions. This dual catalytic approach should also encourage future explorations of both sulfinate and carbene catalysts for new reactions.     

Asymmetric [3+2] Photocycloadditions of Cyclopropanes with Alkenes or Alkynes through Visible‐Light Excitation of Catalyst‐Bound Substrates

The herein reported visible‐light‐activated catalytic asymmetric [3+2] photocycloadditions between cyclopropanes and alkenes or alkynes provide access to chiral cyclopentanes and cyclopentenes, respectively, in 63–99 % yields and with excellent enantioselectivities of up to >99 % ee. The reactions are catalyzed by a single bis‐cyclometalated chiral‐at‐metal rhodium complex (2–8 mol %) which after coordination to the cyclopropane generates the visible‐light‐absorbing complex, lowers the reduction potential of the cyclopropane, and provides the asymmetric induction and overall stereocontrol. Enabled by a mild single‐electron‐transfer reduction of directly photoexcited catalyst/substrate complexes, the presented transformations expand the scope of catalytic asymmetric photocycloadditions to simple mono‐acceptor‐substituted cyclopropanes affording previously inaccessible chiral cyclopentane and cyclopentene derivatives.     

聚合物负载的手性催化剂和手性试剂和合成及应用

近年来,用聚合物负载的手性催化剂和手性试剂完成的不对称合成反应主要集中在潜手性酮的不对称还原反应;烯烃的不对称双羟基化反应;烯烃的不对称环氧化反应;不对称Ｄｉｅｌｓ－Ａｌｄｅｒ反应和饱和碳原子上的不对称取代反应。就近十年来聚合物负载手性催化剂和手性试剂的合成及应用进行了讨论。