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.     

钯-手性膦配体催化剂在烯烃不对称催化反应中的应用

综述了钯-手性膦配体催化剂在烯烃的不对称氢氰化、不对称羰基化、不对称交叉偶联、不对称氢化硅氢化等方面的研究进展。参考文献36篇。     

Asymmetric synthesis of (+)-tetrahydropseudodistomin

An efficient asymmetric synthesis of (+)-tetrahydropseudodistomin is described. The important synthetic features include a Maruoka asymmetric allylation and a Sharpless asymmetric dihydroxylation as key steps for the generation of chirality at C-2, -4, and -5 of the trisubstituted piperidine ring.     

Highly enantioselective synthesis of organic compound using right- and left-handed helical silica

Highly enantiomerically enriched (up to 96-97% ee) 5-pyrimidyl alkanol was obtained by the addition of diisopropylzinc to pyrimidine-5-carbaldehyde in the presence of the artificially designed chiral inorganic material, right- and left-handed helical silica.     

Rhodium-catalyzed asymmetric 1,4-addition of organometallic reagents

Asymmetric 1,4-arylation and 1,4-alkenylation were achieved with the use of organoboronic acids or their derivatives in the presence of a rhodium catalyst coordinated with ligands of the S-2,2"-bis(diphenylphosphino)-1,1"-binaphthyl (S-binap) type. The scope of this asymmetric addition is very broad: ,-unsaturated ketones, esters, amides, alk-1-enyl phosphonates, and 1-nitroalkenes are efficiently converted into the corresponding 1,4-addition products with enantioselectivity >95%. As shown by NMR spectroscopy, the catalytic cycle of the reaction in water involves three intermediates (aryl- or alkenylrhodium, (oxa--allyl)rhodium, and hydroxorhodium complexes). The asymmetric addition of B-Ar-9BBN and ArTi(OPrⁱ)₃ in aprotic solvents occurs with high enantioselectivity under mild conditions to give the corresponding metal enolates as the 1,4-addition products.     

手性螺环配体的合成及其在不对称催化反应中的应用研究进展

手性螺环配体的合成及其在不对称催化反应中的应用是不对称合成和催化研究中重要的研究领域之一, 一些手性螺环配体被合成出来并成功地应用于不对称催化反应中. 综述了近十年来手性螺环配体的合成及在不对称催化反应中的应用研究进展.     

高效手性膦配体的合成及应用

较为详细地综述了高效、应用广泛的手性膦配体的合成进展，并介绍了其在不对称催化反应中的应用。参考文献49篇。     

手性亚砜的合成及其在不对称合成中的应用

本文综述了手性亚砜的合成。由于亚砜结构上的特征以及与金属离子的络合能力,使手性亚砜在不对称合成中具有强烈的诱导作用,使它成为进行不对称合成的一个手段。本文列举了它在不对称合成中的应用情况。     

手性膦配体的合成及其在不对称催化反应中的应用研究进展

手性膦配体的合成及其在不对称催化反应中的应用一直是不对称有机合成和催 化研究中非常重要的研究领域，大量的单齿、双齿和多齿磷配体被合成出来并成功 地应用于不对称催化研究。综述了近十几年来手性磷配体的研究进展。     

手性氨基醇在不对称催化中的应用及新进展

综述了手性氨基醇作为配体或催化剂在不对称合成中的应用及最新进展。     

烯烃不对称双羟化反应中TentaGel树脂支载的可回收和重复使用的OsO_4催化剂研究

合成了在烯烃不对称双羟化反应中可回收和重复使用的TentaGel支载的OsO_4 催化剂。在DMF溶剂中，TentaGel HLBr与三乙胺反应生成季铵盐，在搅拌下后者与 K_2OsO_4饱和水溶液作用24 h，过滤，得TentaGel-OsO_4催化剂，用去离子水在索 氏提取器中连续提取24 h以除去吸附在TentaGel上未键合的K_2OsO_4。 TentaGel- OsO_4催化剂在反式-二苯乙烯的不对称双羟化反应中化学产率≥80%，立体选择性 ≥93% ee，而且连续使用五次，其催化活性不变。     

新型手性环状胺膦配体的设计合成及在酮的不对称还原中的应用

新型手性配体的设计合成是不对称催化研究的重要内容,其中手性胺膦配体因同时含有"软"的磷原子和"硬"的氮原子而具有丰富的配位化学性能和优秀的不对称诱导能力.本文总结了本研究组最近设计合成的手性环状胺膦配体的制备、表征及其在铁催化酮的不对称还原中的应用.手性1,2-环己二胺与双(2-甲酰基苯基)苯基膦通过[2+2]环缩合反应能够顺利获得手性22元环的亚胺膦配体21,该配体经Na BH4还原后生成大环胺膦配体22.利用手性大环胺膦配体22与Fe3(CO)12原位生成的催化体系,能够高活性、高对映选择性地实现包括杂环芳香酮在内50多种酮的不对称转移氢化和不对称氢化反应,其S/C(底物与催化剂的摩尔比)最高可达5000:1,产物手性芳香醇的光学纯度高达99%ee.     

手性金属Salen配合物在不对称催化中的应用*

手性Salen金属配合物已在不对称催化中得到了广泛的应用。本文主要介绍了可溶性的手性金属Salen配合物在不对称催化反应中的应用以及手性金属Salen配合物固载化研究取得的进展。     

Stereoselective Synthesis of Tetrahydropyran D-Ring of Methyl Sartortuoate

A stereoselective synthesis of functionalized tetrahydropyran D‐ring of methyl sartortuoate ( 1 ) was achieved starting from geraniol in a high yield. Sharpless asymmetric kinetic resolution, asymmetric dihydroxylation as well as asymmetric epoxidation were applied as key steps to establish all the four stereocenters of the D‐ring.     

手性噁唑硼烷的研究进展及其应用

手性噁唑硼烷是不对称合成的重要催化剂, 它可以高产率、高立体选择性地催化酮、内消旋酰亚胺以及亚胺的不对称还原, 催化立体选择性Diels-Alder反应、不对称Mukaiyama缩合反应等重要有机化学反应. 概述了近十年来手性噁唑硼烷在不对称合成中的研究进展以及在合成VB₁₂等多种天然及非天然活性化合物中的应用.     

Engineering Chiral Catalysts through Asymmetric Activation and Super High Throughput Screening (SHTS)

A conceptually new strategy for asymmetric catalysis, namely asymmetric activation, in which a chiral activator selectively activates one enantiomer of a racemic chiral catalyst, and a highly efficient screening system for finding the most effective catalysts, namely super high throughput screening (SHTS), by which the reaction can be conducted in parallel and the ee% of the product is allowed to determine within minutes, are summarized in the present account. It is reasonable to believe that SHTS technique combined with asymmetric activation or deactivation principle will provide a very powerful methodology for finding the new catalysts and the best catalyst tuning for asymmetric reactions.     

Asymmetric Synthesis of Chiral Flavan-3-Ols

Flavan-3-ols are a series of natural products widely present in plants and show versatile biological activities. The structures of such compounds are characterized by owing two adjacent chiral centers and three rings. Their interesting structures and promising biological activities have driven increasing research developments toward the preparation of enantioenriched flavan-3-ols. This review summarizes the recent approaches for the asymmetric synthesis of chiral flavan-3-ols from two strategies in the construction of chiral centers. The key steps in the synthetic protocol involve Sharpless asymmetric dihydroxylation, Shi asymmetric epoxidation and Sharpless asymmetric epoxidation.     

不对称催化合成中手性膦配体的研究进展(Ⅰ)(待续)

对近十多年来不对称催化合成领域中出现的手性膦配体进行了综述,按其不对称中心以及结构上的特征加以分类,并对其催化性能进行总结。     

不对称催化反应在手性农药不对称合成中的一些应用

近十多年来，不对称催化反应在单一手性农药研发中的应用渐渐引起人们的关 注，结合自己的研究对这一领域的不对称催化反应及手性催化剂的发展进行了归纳 总结。