氯化N-(3-长链烷氧-2-羟)丙基-N,N,N-三甲基铵的合成及其相转移催化性能

氯化Ｎ┐（３┐长链烷氧┐２┐羟）丙基┐Ｎ，Ｎ，Ｎ┐三甲基铵的合成及其相转移催化性能张广友赵淑英王正祥（山东建材学院应用化学系济南２５００２２）关键词脂肪醇季铵盐相转移催化相转移催化剂因能显著降低反应条件和提高反应收率而越来越被重视。ＲｕｔｚｅｎＨｏｒ...     

聚合物固载Ni－Ag双金属催化剂Ⅱ．催化剂的催化性质

聚合物固载Ｎｉ┐Ａｇ双金属催化剂Ⅱ．催化剂的催化性质吴世华朱常英王连邦张松桢（南开大学化学系，天津３０００７１）关键词镍，银，聚合物固载金属催化剂，加氢，燃料电池电极溶剂化金属原子浸渍（ＳＭＡＩ）技术是制备聚合物负载零价金属催化剂的一个非常有用的方法...     

铱(Ⅰ)/铑(Ⅰ)联萘胺Schiff碱(BPMBNDI)络合物催化的不对称氢转移反应研究

铱（Ⅰ）／铑（Ⅰ）联萘胺Ｓｃｈｉｆ碱（ＢＰＭＢＮＤＩ）络合物催化的不对称氢转移反应研究自国甫尹承烈＊（北京师范大学化学系１００８７５）近年来，一些含氮手性配体的过渡金属催化剂在均相不对称氢硅烷化反应和不对称氢转移反应中已获得广泛应用［１］。在这两类反...     

相转移催化合成增塑剂BBP和水杨醛的研究

相转移催化合成增塑剂ＢＢＰ和水杨醛的研究郭锡坤，高文华，曾东宇（汕头大学化学系，汕头５１５０６３）关键词相转移催化，季铵盐，聚乙二醇，邻苯二甲酸丁苄酯，水杨醛，增塑剂邻苯二甲酸丁苄酯（增塑剂ＢＢＰ）是一种优良的增塑剂．邻羟基苯甲醛（水杨醛）不仅是重要...     

有机锡催化酯交换反应合成羧酸酯的研究

有机锡催化酯交换反应合成羧酸酯的研究田来进，傅芳信，田君濂，刘树祥（曲阜师范大学化学系曲阜２７３１６５，东北师范大学化学系长春）关键词有机锡，催化，酯交换反应，羧酸酯有机锡化合物是一种近乎中性的均相催化剂，不仅不腐蚀金属设备，而且反应物分子中的其他功...     

十六烷基三甲基溴化铵相转移催化合成N,N—二乙基苯胺的研究

十六烷基三甲基溴化铵相转移催化合成Ｎ，Ｎ－二乙基苯胺的研究田庆伟（大连铁道学院应用化学系大连１１６０２８）关键词十六烷基三甲基溴化铵相转移催化Ｎ，Ｎ－二乙基苯胺中图分类号０６２５．６３１Ｎ，Ｎ－二乙基苯胺是制备染料、药物和彩色显影剂的重要中间体，用途...     

相转移催化芳基亚磺酸盐S-烷基化合成砜的研究

相转移催化芳基亚磺酸盐Ｓ－烷基化合成砜的研究李毅群（暨南大学化学系广州５１０６３２关键词相转移催化剂Ｓ－烷基化砜合成中图分类号Ｏ６２３．８３砜基作为活化官能团能在温和条件下引入和除去，因此砜作为有机合成中间体越来越受到重视［１］。砜可以从硫醚氧化得到...     

氧化物－NaZSM－5催化剂的研究Ⅲ．ZrO_2－NaZSM－5催化剂的表征和催化性能

氧化物┐ＮａＺＳＭ┐５催化剂的研究Ⅲ．ＺｒＯ２┐ＮａＺＳＭ┐５催化剂的表征和催化性能杨民（大连铁道学院应用化学系，大连１１６０２８）徐柏庆（大连理工大学化工学院化学系，大连１１６０１２）关键词ＺＳＭ－５沸石，氧化锆，强相互作用，乙醇，正丙胺，催化转化...     

苯乙烯的单电子转移活性自由基聚合

以2,2-二溴甲基-1,3-二溴丙烷（PEBr4）为引发剂,Cu0粉/三（2-二甲氨基乙基）胺（Me6-TREN）为催化体系,在二甲亚砜（DMSO）和H2O的混合溶剂中实现了苯乙烯（St）的单电子转移活性自由基聚合（SET-LRP）。 通过1H NMR和GPC分析表明,所得聚合物为星形结构并具有较窄的分子量分布Mw/Mn=1.20（MGPCn=25.3×103,转化率为42.6%）,且聚合物的链端保留了-Br端基。 考察了溶剂、反应温度及相转移催化剂对聚合的影响,结果表明,混合溶剂中H2O的体积分数由10%增加至20%导致了聚合速率的降低,表观聚合速率常数（kappp）由0.026 4 h-1减小至0.019 7 h-1;升高反应温度、增加催化剂用量以及相转移催化剂的加入分别导致聚合体系的kappp增加,同时,催化剂用量的增加和相转移催化剂的加入使聚合物的分子量分布系数降低。     

聚合物负载的相转移催化剂作用下的潜手性酮不对称还原

本文在苯乙烯－二乙烯苯共聚物上负载了奎宁，辛可宁，Ｄ－（一）－麻黄碱制备胺盐型相转移催化剂，对一系列苯基烷基潜手性酮的硼氢化还原反应进行了不对称催化。研究了负载不同生物碱的催化剂，不同的潜手性酮，不同的反应温度及不同的有机介质对反应的化学收率及光学产率的影响对反应要进行一定的探讨。     

Stereodivergent Construction of 1,3-Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction

Herein, we report a synthesis of cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition of dialkylzinc reagents to cyclic enones with iridium-catalyzed asymmetric allylic substitution reaction. Good to excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction of adjacent stereocenters (1,2-position) reported in the literature, the current reaction can achieve the stereodivergent construction of nonadjacent stereocenters (1,3-position) by a proper combination of two chiral catalysts with different enantiomers.     

Enantioselective hydrogenation of alpha-aryloxy alpha,beta-unsaturated acids. Asymmetric synthesis of alpha-aryloxycarboxylic acids

[reaction: see text] A facile preparation of chiral alpha-aryloxy carboxylic acids via asymmetric hydrogenation of the corresponding unsaturated acids has been discovered. A number of catalysts have been identified that give high product enantioselectivity, and the scope of the reaction has been examined with respect to substitution on the aromatic ring and olefin.     

N-Prolinylanthranilic acid derivatives as bifunctional organocatalysts for asymmetric aldol reactions

Several N-prolinylanthranilic acid derivatives were prepared and tested as bifunctional organocatalysts in the direct asymmetric aldol reaction of cyclohexanone with p-nitrobenzaldehyde. It was found that methyl substitution ortho to the carboxylic acid improves enantioselectivity, but substitution ortho to the anilide group does not. The catalyst derived from 2-amino-6-methylbenzoic acid was tested over a range of direct asymmetric aldol reactions and its overall performance is equal to or better than many of the known prolinamide catalysts in terms of yield, diastereoselectivity, and enantioselectivity.     

Synthesis of new chiral thiazoline-containing ligands

New chiral ligands, including bi- and tridentate thiazoline derivatives, analogues of known oxazolines, have been synthesized by a general and convenient procedure, starting from dithioesters and commercial enantiopure 2-aminoalcohols. A preliminary test shows the ability of such ligands to act as asymmetric catalysts in Pd-catalyzed allylic substitution reaction.     

不对称Henry反应的研究进展

总结了各种能有效催化不对称Henry反应的新方法、新条件和新催化剂,讨论了一类拓展的不对称催化Henry反应。对立体选择性催化Henry反应的催化剂的发展提出了作者的一些看法。参考文献26篇。     

Improved asymmetric S(N)Ar reaction of beta-dicarbonyl compounds catalyzed by quaternary ammonium salts derived from cinchona alkaloids

The scope and limitation of the asymmetric nucleophilic aromatic substitution reaction of alpha-substituted 1,3-dicarbonyl compounds and activated aromatic systems catalyzed by N-benzyl-O-benzoylcinchoninium or cinchonidinium salts are presented. Several novel O-benzoylcinchona alkaloid derived salts have been prepared and evaluated as catalysts in this reaction, which can proceed with enantioselectivites up to 96% ee. Various 1,3-dicarbonyl compounds and activated aromatic systems are evaluated for the aromatic nucleophilic substitution reaction, and it has been found that the yield and enantioselectivity are very dependent on the substrate and reagent. The scope of the functionalization of the products to, e.g., spiro-oxoindole, a ring-opening reaction of 1,3 alpha,alpha-disubstituted dicarbonyl compounds with several nucleophiles, and the diastereoselective reduction of the keto functionality in the optically active S(N)Ar product are reported.     

Asymmetric Cu-catalyzed Henry reaction using chiral camphor Schiff bases immobilized on a macromolecular chain

Immobilized catalysts have attracted chemists’ attention for long time because of convenient recycling, which is very important for some special catalyst even immobilizations accompanying the decrease of catalytic activity and selectivity. Our group focused on the developing chiral catalysts with camphor framework to catalyze various asymmetric reactions for long time. For easily recycling the unique chiral catalysts, a series of polymer catalysts with chiral camphor unit were synthesized by RAFT polymerization. Herein, the performance of the synthesized polymer chiral catalysts was reported by catalyzing asymmetric Henry reaction. After optimizing the reaction conditions, the synthesized chiral polymer catalyst provides a good yield and enantioselectivity to the reaction of p-nitrobenzaldehyde and nitromethane. In the meantime, the recycles and reused properties of synthesized polymer catalysts were examination by the model asymmetric Henry reaction. The catalyzed activities and enantioselectivities did not show obviously decrease until recycling five times.     

Fluorinated chiral secondary amines as catalysts for epoxidation of olefins with oxone

We have synthesized a series of chiral cyclic secondary amines having different substitution patterns and have screened them as catalysts for the asymmetric epoxidation of olefins using Oxone. The highest enantiomeric excess (61%) occurred for the epoxidation of 1-phenylcyclohexene catalyzed by a secondary amine bearing a fluorine atom at the beta-position relative to the amino center. Our experimental results provide further support to the notion that the amine plays a dual role--as a phase transfer catalyst and an Oxone activator--in these epoxidation reactions. The slightly acidic reaction conditions we employed in this work obviate the need to preform ammonium salts, which are the actual catalysts that mediate the epoxidations.     

手性相转移催化剂及其不对称催化反应

综述了手性季铵盐和手性冠醚两类手性相转移催化剂及其在不对称催化反应（包括加成，取代，氧化及还原等反应）中的应用，参考文献９７篇。     

钯催化烯丙基取代反应中手性配体的"甲基效应"

作为含氮手性配体研究的一部分［1］,最近我们报道了手性含氮双齿配体2(结构如Scheme 1所示)的设计合成及其在铜催化下的不对称环丙烷化反应中的应用［2］.