手性稀土配合物催化的亚膦酸酯对醛的不对称加成（Pudovik）反应研究

手性稀土配合物催化的亚膦酸酯对醛的不对称加成（Ｐｕｄｏｖｉｋ）反应研究钱长涛黄太生（中国科学院上海有机化学研究所金属有机化学开放实验室上海２０００３２）关键词对映选择性加成Ｐｕｄｏｖｉｋ反应手性镧配合物α－羟基膦酸酯分类号Ｏ６４３．３２光学纯的α－羟...     

手性磷酸催化芳香胺与硝基烯烃的不对称加成反应

以轴手性联萘酚为原料,合成了一系列手性磷酸催化剂,并首次将其应用于催化芳香胺和硝基烯烃的不对称氮杂迈克尔加成反应中,产物β-硝基胺的产率和对映选择性分别达65％～95％和16％～70％.     

手性联萘酚锂盐催化下三甲基硅氰与芳香醛的对映选择加成反应研究

光学活性芳香氰醇及其衍生物是合成一些具有重要生理活民生天然产物的关键中间体。氰基醇的对映选择合成主要是利用由光学活性手性配体与甲价钛形成的配合物为手性催化剂,催化醛与氢氰酸或三甲基硅氰（TMSCN）的加成,由于手性联萘酚（BINOL）在很多反应中表现出优异的立体选择催化活性,故试图用其催化醛与氢氰酸或TMSCN的加成,但对映选择性不理想,我们用BINOL与正丁基锂作用生成的盐催化芳香醛与TMSCN的对映选择加成,取得了较好的结果。     

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。     

手性金属配合物应用于不对称Henry反应研究进展

手性β-硝基醇化合物是一类用途广泛的双官能团化合物，不对称Henry加成反应是制备手性β-硝基醇化合物最有效的方法之一，同时该反应在构建碳-碳键的过程中具有优异的原子经济性。在不对称Henry加成反应中，手性催化剂起到至关重要的作用，近年来围绕这一课题取得了许多重要进展。本文将从手性金属配合物中的铜配合物、锌配合物、稀土金属配合物、锰配合物以及钴配合物等多方面综述金属配位型催化剂在不对称催化Henry反应中的研究进展，并对其未来的发展前景进行了展望。      

对硝基苯磺酰基乙酸酯与α，β－不饱和酸酯类化合物在固液相转移条件下的反应

在固液相转移催化（Ｋ_２ＣＯ_３／ＤＭＦ／ＴＥＢＡ）条件下，对硝基苯磺酰基乙酸酯与α，β－不饱和酸酯反应意外地生成加成重排产物［如生成２－甲基－２－（对硝基苯基）戊二酸－１－甲酯－５－乙酯］。其反应机理可能是砜酯首先与α，β－不饱和酯起Ｍｉｃｈａｅｌ反应，随后加成物发生分子内芳环上的亲核性取代，酸化后脱去ＳＯ２得最终产物。     

磷杂螺环化合物的合成──3，9－二氢－3，9－二硫代－2，4，8，10－四氧杂－3，9－二磷杂螺环［5，5］十一烷的合成及其与α－芳基－β－硝基烯的加成反应

本文合成了３，９－二氢－３，９－二硫代－２，４，８，１０－四氧杂－３，９－二磷杂螺环－［５，５］十一烷２，研究了２在Ｎ，Ｎ－二甲基乙酰胺介质中，在氢化钠作用下与α－芳基－β－硝基烯的加成反应，得到５个新的加成产物３_（ａ－ｅ），对２及加成物３_（ａ－ｅ）的~１ＨＮＭＲ谱进行了归属，并得到元素分析和ＩＲ的证实。     

（3S）—β—羟基丁酸的合成

以光学活性Ｌ－乳酸为原料，经还原得（２Ｓ）－１，２－丙二醇（２），再经亚硫酰环化、亲核加成及酸解反应，得到手性合成子（３Ｓ）－β－羟基丁酸，收率５８．４％（以的２计），光学纯度大于９０％。     

手性双氮氧化物-La(OTf)3络合物高对映选择性催化硝基烷烃对 硝基烯的Michael加成反应研究

手性1,3-二硝基化学物的合成已引起化学家极大的兴趣, 主要因为它衍生形成的1,3-二胺是合成药物的重要中间体, 但是合成该化合物的不对称催化反应在近几年才兴起. 四川大学化学学院冯小明等基于他们课题组的手性氮氧骨架已经在不对称合成中获得了很好的应用效果, 同时由于镧化学在有机合成领域有很好的前景, 因此设计了La(OTf)3和手性氮氧的络合物催化剂来催化硝基化合物对硝基烯烃的Michael加成, 得到了具有相邻两个手性中心的高光学纯度的1,3-二硝基化合物, 在较温和的反应条件下实现了了高区域选择性(高达93∶7)和高对映选择性(高达97% ee). 该研究具有催化剂易得、反应高效、操作简单、反应条件温和的特点.     

天然产物Divergolide A手性甲基酮片段（C4-C10）的合成

手性甲基酮片段（C4-C10）是天然产物Divergolide A的重要组成部分。分别采用3种方法实现了该片段的合成。第一种方法包含手性丁酸衍生物的常规不对称烷基化反应及后续反应等8步反应，总收率42%；第二种方法包含手性辅基诱导的手性丁酸衍生物的迈克尔加成反应和选择性维悌希反应等4步反应，总收率58%；第三种方法包含二苯基脯氨醇甲醚催化的甲基乙烯基酮的迈克尔加成反应和选择性维悌希反应等两步反应，总收率67%。产物结构经¹H NMR, ¹³C NMR和HR-MS(EI)确证。      

Palladium oxide nanoparticles supported on graphene oxide: A convenient heterogeneous catalyst for reduction of various carbonyl compounds using triethylsilane

Palladium oxide nanoparticles supported on graphene oxide ‐ triethylsilane was found to be an effective reductive system for a broad range of reduction processes, including the reduction of various carbonyl compounds such as aromatic aldehydes to their corresponding alcohols or methyl arene compounds, aromatic ketones to their respective alcohols or saturated compounds, aromatic acyl chlorides to their reduced compounds. The desired products were obtained in good to excellent yields under mild conditions. The heterogeneous environmentally friendly catalyst can be easily separated from the reaction mixture through a simple filtration, facilitating purification of the prepared compounds.     

Library of second-generation cycloruthenated compounds and evaluation of their biological properties as potential anticancer drugs: passing the nanomolar barrier

A library of 32 organoruthenium compounds has been synthesised. Known and novel C-N cyclometalated compounds as well as N-C-N and N-N-C pincer derivatives of this metal have been used in this purpose. Most of the compounds have been tested for their in vitro antitumoral behaviours, good to excellent activities have thus been found. Several of the newly synthesized compounds pass the symbolic barrier of the nanomolar range for their IC(50) indicating a critical improvement. The level of activity is tentatively correlated to physicochemical properties of the compounds such as their Ru(III/II) redox potential and their lipophilicity (log P).     

三脚架结构化合物及其配合物研究进展

本文按三脚架结构化合物中心部分构成的不同。分四类对配体及其配合物的结构,性能进行了介绍。（1）以环为中心的三脚架结构化合物;（2）以氮原子为中心的三脚架结构化合物;（3）以碳原子为中心的三脚架结构化合物;（4）以硼原子及磷原子为中心的三脚架结构化合物。     

Microextraction techniques in the analysis of food flavor compounds: A review

Food flavor compounds due to the complexity of food as a matrix, and usually their very low concentrations in a product, as well as their low odor thresholds, create a challenge in their extraction, separation and quantitation. Food flavor volatiles represent compounds of different polarity, volatility and chemical character, which determine method of extraction for their isolation from food. Microextraction techniques, mainly SPME and SBSE have been used for food flavor compounds analysis for two decades. Microextraction methods other than SPME and SBSE are seldom used despite their analytical potential. The review discusses the nature of food flavor compounds, and different approaches to food flavor analysis. It summarizes the use of microextraction methods in food flavor compounds analysis based on papers published in the last 5 years, and discusses the potential of microextraction methods in this field.     

Synthesis of azobenzenes: the coloured pieces of molecular materials

Azobenzenes are ubiquitous motifs very important in many areas of science. Azo compounds display crucial properties for important applications, mainly for the chemical industry. Because of their discovery, the main application of aromatic azo compounds has been their use as dyes. These compounds are excellent candidates to function as molecular switches because of their efficient cis-trans isomerization in the presence of appropriate radiation. The classical methods for the synthesis of azo compounds are the azo coupling reaction (coupling of diazonium salts with activated aromatic compounds), the Mills reaction (reaction between aromatic nitroso derivatives and anilines) and the Wallach reaction (transformation of azoxybenzenes into 4-hydroxy substituted azoderivatives in acid media). More recently, other preparative methods have been reported. This critical review covers the various synthetic methods reported on azo compounds with special emphasis on the more recent ones and their mechanistic aspects (170 references).     

Methods and algorithms for predicting the properties of chemical compounds by common fragments of molecular graphs

Methods and algorithms for predicting the properties of chemical compounds by common fragments of their molecular graphs are described. The prediction algorithms are based on determination of a measure of structural proximity (distance) between molecular graphs, which depends on the size of their common fragment. The prediction procedure involves the following steps: partitioning the property classes of the training sample compounds into subclasses of structurally similar compounds; seeking structurally typical compounds and their fragments in each subclass; classifying control compounds according to their distances from the training sample compounds or fragments of classes; forming a set of essential fragments of samples potentially responsible for the properties exhibited by the compounds. The algorithms were successfully tested in the BACC system for analyzing and classifying biologically active compounds designed at the Institute of Mathematics, Siberian Branch, Russian Academy of Sciences. S. L. Sobolev Institute of Mathematics, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 1, pp. 113–125, January–February, 1998.     

Dinitroso and polynitroso compounds

The growing interest in the chemistry of C-nitroso compounds (RN=O; R = alkyl or aryl group) is due in part to the recognition of their participation in various metabolic processes of nitrogen-containing compounds. C-Nitroso compounds have a rich organic chemistry in their own right, displaying interesting intra- and intermolecular dimerization processes and addition reactions with unsaturated compounds. In addition, they have a fascinating coordination chemistry. While most of the attention has been directed towards C-nitroso compounds containing a single -NO moiety, there is an emerging area of research dealing with dinitroso and polynitroso compounds. In this critical review, we present and discuss the synthetic routes and properties of these relatively unexplored dinitroso and polynitroso compounds, and suggest areas of further development involving these compounds. (126 references.).     

Combinations of natural and synthetic inclusion compounds and their thermal stability

Inclusion compounds do not belong to the group of simple compounds. They consist of molecules of the host and guest components. Some of them form supermolecules and exhibit super-molecular properties.Combinations of inclusion compounds as even more complicated systems need more methods to be used for their identification. Thermoanalytical study enables to study the sorption during their formation and the progressive liberation of their individual components and parts. Many layered silicates, phosphates and other similar synthetic and natural compounds enclosing or adsorbing cyclodextrins, pharmaceuticals, aromatics, various agrochemicals and inorganics are analysed from the view of their formation and properties.     

Polyhedral structures with an odd number of vertices: nine-coordinate metal compounds

The stereochemistry of nine-coordinate transition-metal and rare-earth compounds has been studied by means of continuous shape measures (CShM) and related tools. Several reference nine-vertex polyhedra have been defined and their minimal distortion interconversion paths established. A theoretical shape map is presented in which the structures can be placed according to their distances in CShM space to the capped square antiprism and the tricapped trigonal prism, which are the most common polyhedra in nine-coordinate compounds. The structures of almost 2000 metal coordination spheres in molecular and extended solid-state compounds have been analyzed. Clear stereochemical trends can be established for subsets of these compounds grouped according to the nature of their ligands, which include families of compounds spread along the interconversion paths between the capped square antiprism and the capped cube, or between the tricapped trigonal prism and the tridiminished icosahedron.     

氮氧自由基的应用研究进展

氮氧自由基化合物是指含碳、氮、氧、氢等元素以及自旋单电子的有机化合物,因其自身的特殊性质被广泛应用于很多领域。本文结合氮氧自由基的特点,对其在生物学、磁性、有机催化和阻聚等方面的应用研究进行了总结,并对氮氧自由基化合物的发展趋势进行了展望。