炔基锌与醛的催化不对称加成反应研究进展

光学活性的炔丙醇是一类很重要的手性合成砌块,而末端炔对醛的不对称亲核加成是合成手性二级炔丙醇非常有效的方法.以手性配体的结构类型为依据,综述了炔基锌试剂对醛的不对称加成反应的研究进展.     

手性二茂铁膦配体在不对称催化反应中的应用

综述了手性坏茂铁膦配体的过渡金属配合物催化不对称氢化、硅氢化、交叉偶联、环加成、Ａｌｄｏｌ等反应的最新进展,参考文献５６篇。     

手性二茂铁类配体在钯催化不对称反应中的应用

本文综述了近10 年来手性二茂铁类配体在钯催化不对称烯丙基取代反应,包括各种不同底物的烯丙基烷基化、烯丙基胺基化和烯丙基磺酰化反应中的应用,并对其在不对称Claisen 重排、不对称Diels-Alder 反应、不对称Heck 反应、不对称羰基化、不对称氢化硅烷化和不对称碳碳键断裂等反应中的应用进行了综述,对部分反应的机理和该领域的发展前景进行了讨论。     

基于甲磺酰基的磺酰胺-氨醇作为催化醛的不对称炔基化反应新配体

 以商业易得的 (–)-麻黄碱、(+)-伪麻黄碱和各种手性氨醇为主要原料, 经过简单的两步反应, 合成了一系列基于甲磺酰基的磺酰胺-氨醇 (SAA) 配体, 并将其用于催化苯乙炔基锌对醛的不对称加成反应. 在没有 Ti(OiPr)4 等金属试剂的条件下, 配体表现出较好的不对称诱导能力, 取得了高达 83% ee.     

手性联二萘酚衍生物催化的苯乙炔与苯甲醛不对称加成反应

以手性联二萘酚为原料,合成了3,3′位取代的手性联二萘酚衍生物,研究了该衍生物配体在二乙基锌存在下,催化苯乙炔与苯甲醛的不对称加成反应,产物的产率为73%,e.e.值为40%。 研究结果表明,手性联二萘酚衍生物结构的微小变化导致催化产物构型的改变。     

手性氨基醇衍生物催化苯基锂与亚胺的不对称加成反应研究

本文报道几种不同结构的手性氨基醇衍生物在亚胺与苯基锂不对称加成反应中的应用,并对配体结构与对映选择性的关系进行了初步探索,研究结果表明,在双手性配体中,具有反式(S,S)构型的配体催化效果优于顺式(S,R)。     

配体参与的有机金属化合物对亚胺的不对称加成反应

手性胺类化合物是一类重要的有机化合物,在生物化学及药物合成中有广泛应用.有机金属化合物对亚胺的不对称加成反应是合成手性胺类化合物的重要方法之一.本文对近年来外加配体参与的有机金属化合物对亚胺的不对称加成反应,特别是催化合成手性胺类化合物的研究进展作一概述.     

手性钛衍生物催化的有机金属试剂的不对称加成反应

对手性钛衍生物作为路易斯酸催化的几种有机金属试剂与羰基化合物的不对称加成反应进行了综述。     

手性二茂铁基膦氧配体-铜络合物催化的二乙基锌对β-芳基硝基烯的不对称共轭加成反应

研究了手性二茂铁基膦氧配体.铜络合物催化的二乙基锌对β-芳基硝基烯的不对称加成反应,在优化的反应条件(8(mol)%配体和6(mol)%的Cu(OTf)2,以甲苯为溶剂,在-30℃下反应12h)下,取得了最高77%的产率和58%的ee值.     

二茂铁衍生的手性硫膦配体在铱催化喹啉不对称氢化中的应用

 Chiral S,P-donor ferrocene-derived ligands were synthesized and applied in the asymmetric hydrogenation of quinolines using the ［Ir(COD)Cl］2/S,P-ligand complex as the catalyst in the presence of iodine. The effects of the solvent and hydrogen pressure on conversion and enantioselectivity were examined, and up to 82% ee was obtained. The planar chirality plays an important role in this reaction. R- and S-enantiomers of 1,2,3,4-tetrahydroquinoline derivatives were obtained using ligands 3 and 5, respectively.     

手性氨基醇催化的苯乙炔与酮的对映选择性加成

(S)-(1-Benzylpyrrolidin-2-yl)diphenylmethanol and cinchonine were evaluated as promotors in the asymmetricadditions of phenylacetylene to ketones,in order to prepare chiral propargylic alcohols.Good yields(up to 89%)and moderate enantioselectivities(up to 77.9% ee)were achieved.Addition of Ti(OPr-i)_4 can significantly improvethe enantioselectivity of the reaction.     

从脯氨酸合成一种三齿手性配体及其在二乙基锌对醛的对映选择性加成中的应用

A new chiral tridentate ligand [1-(1-methyl-S-pyrrolidin-2-ylmethyl)-S-pyrrolidin-2-yl]-diphenylmethanol (1) has been successfully synthesized from S-proline. The structure of the ligand was characterized by NMR spectra and X-ray diffraction analysis. Its catalytic ability has also been examined in enantioselective addition of diethylzinc towards aldehydes with 15%-84% enantiomeric excesses (ee).     

醛与有机锌的不对称加成反应机理研究进展

醛与有机锌试剂的加成反应是近年来醛不对称加成研究的热点.本文综述并讨论了该类体系的两大类反应机理的微观过程,分析了两大类机理的根本不同之处.     

Enantioselective Alkynylation of Benzaldehyde Catalyzed by New Chiral Lewis Acid Ligand: Zinc-Amide Complex

The enantioselective alkynylzinc addition to aldehydes is very useful for the synthesis of chiral propargyl alcohols which are important versatile building blocks of many biologically active compounds and natural products1. A series of chiral oxazolidines were conveniently synthesized from amino acids in three steps with good yields. The use of chiral Lewis acid ligand: zinc-amide complex in situ generated from this oxazolidine with alkylzinc as chiral catalysts for the enantioselective alkyny…     

Enantioselective Addition of Diethylzinc to Aromatic Aldehydes Catalyzed by New Chiral Oxazolidine Ligand

Abstract

The chiral oxazolidine ligand can catalyze the enantioselective addition of diethylzinc to aromatic aldehydes at room temperature with high enantioselectivity (98–99% ee). The conditions for this catalytic process are both mild and simple as compared with the same kind catalyst.     

Synthesis of Novel 1,4‐Bissulfonamide Ligands for Enantioselective Addition of Diethylzinc to Aldehydes

Several novel chiral sulfonamide ligands based on (1R,2S,4R,5S)‐1,4‐diamino‐2,5‐dimethylcyclohexane skeleton have been synthesized and their application in the enantioselective addition of diethylzinc to aldehydes was investigated in the presence of Ti(OⁱPr)₄. The effect of ligands, temperature and the loading amount of ligands was studied. Under optimized conditions, enantioselective addition of diethylzinc with various aryl aldehydes and aliphatic aldehydes proceeded smoothly and afforded chiral secondary alcohols in up to 88% ee.     

联萘衍生物作为手性配体在二烷基锌和醛不对称加成反应中的应用

光学活性的联萘衍生物作为优异的手性配体应用到不对称催化中已取得了巨大进展,显示出广阔的应用前景,综述了近年来联萘衍生物小分子、树枝状大分子和高分子作为手性配体和其金属络合物作为手性催化剂在二烷基锌和醛不对称加成反应中的应用.     

含硫手性配体催化的有机锌试剂在不对称加成反应中的最新研究进展

按配位原子的数目和种类进行分类, 综述了近年来含硫的手性配体在有机锌试剂和醛等化合物的不对称加成反应中的最新研究进展.     

Development of Highly Active Chiral Titanium Catalysts for the Enantioselective Addition of Various Organometallic Reagents to Aldehydes

The catalytic enantioselective carbonyl addition reaction has long attracted the interest of chemists because of its synthetic importance. Although many highly enantioselective reactions have been developed, with few exceptions the reactions are carried out at relatively high catalyst loadings, making them less practical for scale‐up applications. In addition, organometallic reagents employed as carbon nucleophiles have been limited to those with relatively low reactivity, such as diorganozincs and arylboronic acids. In an effort to enhance the practicality, a highly active and enantioselective chiral titanium catalyst system was recently developed in our laboratory, enabling the enantioselective carbonyl addition reaction to aldehydes using various organometallic reagents (RM; M = MgX, Li, BY₂, ZnX, AlMe₂) at lower catalyst loadings (≤5 mol %).