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Salen-Cu(Ⅱ)和唑啉-Cu(Ⅱ)配合物催化2-苯基环己酮的不对称Baeyer-Villiger反应研究

对一系列手性Salen和唑啉配体与中心金属Cu(Ⅱ)的配合物催化2-苯基环己酮的不对称Baeyer-Villiger反应进行了研究,设计和合成了新型手性配体Ⅲ,Ⅳ, Ⅴ,对配合物Ⅴ-Cu(Ⅱ)进行了单晶X射线衍射分析. 并考察了助氧化剂、溶剂等对反应活性和选择性的影响.     

手性不对称Salen Ni配合物的模板法合成及表征

本文采用过渡金属镍(Ni)作为金属模板合成了2个未见报道的手性不对称Salen Ni配合物，该法具有反应步骤少、纯化处理简单、产率高的显著优点。用¹H NMR、FTIR、UV-Vis、CD光谱及元素分析对配合物进行了详细的表征，证明该模板合成法的可靠性。此外，对该法合成的手性不对称Salen Ni配合物的红外光谱、电子吸收光谱、圆二色光谱的性质做了进一步研究。     

手性Salen-Cu(Ⅱ)和噁唑啉-Cu(Ⅱ)配合物催化2-苯基环己酮的不对称Baeyer-Villiger反应研究

对一系列手性Salen和唑啉配体与中心金属Cu(Ⅱ )的配合物催化 2 苯基环己酮的不对称Baeyer Villiger反应进行了研究 ,设计和合成了新型手性配体Ⅲ ,Ⅳ ,Ⅴ ,对配合物Ⅴ Cu(Ⅱ )进行了单晶X射线衍射分析 .并考察了助氧化剂、溶剂等对反应活性和选择性的影响 .     

手性Salen—Cu（II）和Wu唑啉—Cu（II）配合物催化2—苯基环已酮的不对称Baeyer—

对一系列手性Salen和Wu唑啉配体与中心金属（Cu（II）的配合物催化2－苯基环已酮的不对称Baeyer-Villiger反应进行了研究,设计和合成了新型手性配体III,IV,V,对配合物V－Cu（II）进行了单晶X射线衍射分析,并考察了助氧化剂,溶剂等对反应活性和选择性的影响。     

双功能金属锌(Salen)配合物催化的醛的不对称炔基加成反应

本文研究了双功能金属锌(Salen)配合物催化的醛的不对称炔基加成反应。在相应的反应中,当手性salen配体的C3和C3’位有路易斯碱性的1-哌啶甲基取代时,其和金属锌形成的配合物较一般的锌(Salen)配合物具有更好的催化活性和立体选择性。     

手性Salen-Co(Ⅱ)络合物催化芳香酮的不对称还原反应 ——推荐一个综合化学实验

介绍以Salen—Co（Ⅱ）络合物为金属有机催化剂的不对称芳香酮还原反应实验。通过本实验可了解有关手性、金属配合物催化剂的设计合成、催化机理、产率、选择性等基本概念，提高在手性化合物拆分及不对称催化方面的操作能力，加强在有机、无机合成、仪器分析、催化、手性分离及化合物表征等方面的综合能力。讨论了该实验在高年级本科生综合化学实验教学工作中的实践效果。     

手性席夫碱及其金属配合物作为手性催化剂的某些应用

简要介绍和评述了近15年来手性Schiff碱及其金属配合物作为手性催化剂, 在不对称氢化、不对称氢转移、不对称氢硅化、不对称硅氰化和不对称氢氰化等反应中的应用研究进展.     

手性席夫碱配合物用于催化不对称环氧化

手性席夫碱过渡金属配合物可以高效催化烯烃不对称环氧化反应,因此其合成及催化性能研究一直以来受到广泛的关注.本文较详细地综述了最近十年来合成的手性席夫碱过渡金属配合物及其对烯烃环氧化反应的催化性能的研究进展.重点讨论了新型的对称和非对称salen型配体过渡金属配合物的合成及其应用,分析探讨了手性席夫碱过渡金属配合物作为催化剂的优缺点、催化机理和未来发展方向.     

C2型轴对称手性双噁唑啉的合成及其应用研究

本文综述了手性双恶唑啉的合成及其金属配合物作为手性催化剂在催化不对称反应中的应用研究进展。     

手性1，4-二胺构建的双核铜[2+2]席夫碱大环化合物：制备和催化研究

Dinuclear copper(Ⅱ) complexes of [2+2] macrocyclic Schiff bases have been prepared from chiral 1,4-diamines using sodium ions as template. Catalytic investigation on the titled complexes has been carried out on model reactions (asymmetric sulfoxidation and asymmetric oxidative-coupling reactions).     

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。     

Diels-Alder反应在不对称合成中的研究进展

狄尔斯-阿尔德（DA）反应自被发现以来，在有机经学中占有重要地位。对近 年来DA反应不对称合成催化剂（尤其是手性Lewis酸化合物）、手性助剂和手性双 烯三个主要方面的研究进展进行了讨论。     

Asymmetric Catalysis with Heterobimetallic Compounds

This review focuses on a new concept in catalytic asymmetric reactions that was first realized for the use of heterobimetallic complexes. As these heterobimetallic complexes function as both a Brønsted base and as a Lewis acid, just like an enzyme, they make possible a variety of efficient catalytic asymmetric reactions. This heterobimetallic concept should prove to be applicable to a variety of new asymmetric catalyses. The first part of this review describes the development of rare-earth–alkali metal complexes such as LnM₃tris(binaphthoxide) complexes (LnMB, Ln = rare-earth metal, M = alkali metal), which are readily prepared from the corresponding rare-earth trichlorides or rare-earth isopropoxides, and their application to catalytic asymmetric synthesis. By using a catalytic amount of LnMB complexes several asymmetric reactions proceed efficiently to give the corresponding desired products in up to 98% ee: LnLB-catalyzed asymmetric nitroaldol reactions (L = Li), LnSB-catalyzed asymmetric Michael reactions (S ? Na), and LnPB-catalyzed asymmetric hydrophosphonylations of either imines or aldehydes (P ? K). Applications of these heterobimetallic catalysts to the syntheses of several biologically and medicinally important compounds are also described. Spectral analyses and computational simulations of the asymmetric reactions catalyzed by the heterobimetallic complexes reveal that the two different metals play different roles to enhance the reactivity of both reaction partners and to position them. From mechanistic considerations, a useful activation of the heterobimetallic catalyses was realized by addition of alkali metal reagents. The second part describes the development of another type of heterobimetallic catalysts featuring Group 13 elements such as Al and Ga as the central metal. Among them, the AlLibis(binaphthoxide) complex (ALB) is an effective catalyst for asymmetric Michael reactions, tandem Michael–aldol reactions, and hydrophosphonylation of aldehydes.     

Asymmetric Amplification in the Catalysis with Chiral Lanthanide Complexes

Remarkably high asymmetric amplifications (positive nonlinear effects) were realized in some chiral lanthanide complex-catalyzed organic reactions such as the asymmetric hetero-Diels–Alder reaction, Michael addition reaction, epoxidation, etc. These phenomena may be explained by the autogenetic formation of the enantiopure lanthanide complexes as the most active catalysts. The high coordination numbers of the lanthanides seem to play an important role through the formation of aggregates of the heterochiral complexes as less active catalysts.     

新型手性稀土配合物的合成、表征及其在不对称催化反应中的应用

作为符合绿色化学标准的稀土三氟甲磺酸盐Ln(OTf)3化合物打破了传统路易斯酸催化的模式，以其在水中稳定、催化用量少(一般少于10 mol％)和可回收再用的独特性质而受到广泛关注。Ln(OTf)3化合物可以催化许多有机合成反应，得到多种多样重要的合成中间体。但是，到目前为止，手性     

Bis(oxazolinyl)phenyl transition metal complexes: synthesis, asymmetric catalysis, and coordination chemistry

Molecular catalysts for organic synthesis should be constructed to be tailored to target reactions and their desirable conditions. In our search for them, we have studied new types of transition metal molecular catalysts dressed with a tridentate N,C,N modular ligand, which consists of a C2-symmetric side-by-side phenyl group with chiral bis(oxazolinyl) substituents. The ligand, 2,6-bis(oxazolinyl)phenyl abbreviated as Phebox, can connect covalently to transition metals by the central carbon atom. Here, we review our recent work on the chemistry of Phebox and its metal complexes, including preparation, structural analysis, asymmetric Lewis acid catalysis, asymmetric hydrosilylation, asymmetric conjugate reduction, asymmetric reductive aldol reaction, and organometallic reactions.     

末端炔与亚胺及衍生物的不对称加成反应研究进展

总结了近年来关于末端炔与亚胺及衍生物的不对称加成反应的研究进展,包括小分子均相催化体系与固载化的手性催化剂.其中小分子均相催化体系主要有:Pybox-铜、手性二胺-铜、Quinap-铜、Pinap-铜、磺酰胺亚胺-铜、二肽类-镐、氨基醇-锌等.另外,还讨论了末端炔、醛与胺的多组分反应的研究.     

Enantioselective Iron‐Catalyzed Intramolecular Cyclopropanation Reactions

An iron‐catalyzed asymmetric intramolecular cyclopropanation was realized in high yields and excellent enantioselectivity (up to 97 % ee) by using the iron complexes of chiral spiro‐bisoxazoline ligands as catalysts. The superiority of iron catalysts exhibited in this reaction demonstrated the potential abilities of this sustainable metal in asymmetric carbenoid transformation reactions.     

含二茂铁和吡啶单元的手性席夫碱配体在钌催化的不对称氢转移反应中的应用

Chiral Schiff base complexes are very efficient for a wide range of reactions, including expoxidation[1], epoxide ring opening[2], Diels-Alder reaction[3], aldol reaction[4], etc. However, there are only few examples of P-N chelate Schiff bases being used as the chiral ligands in the asymmetric transfer hydrogenation of ketones. Recently, Gao et al[5] reported a series of P,N,N,P Schiff base ligands that have relatively low enantioselectivity in the asymmetric transfer hydrogenation of ketones.