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机构地区:[1]昆明理工大学化学工程学院,云南昆明650500
出 处:《化工进展》2016年第2期485-492,共8页Chemical Industry and Engineering Progress
基 金:国家自然科学基金项目(21266012)
摘 要:不对称催化氢化反应具有完美的原子经济性和清洁高效等特点,是最受青睐的不对称合成方法之一。C=C、C=O、C=N的不对称加氢反应仍主要依赖过渡金属催化剂。过渡金属催化剂,尤其是铑催化剂,催化碳碳双键的不对称加氢反应仍是一个不断发展的领域。本文对近年来利用铑催化剂催化烯烃进行不对称氢化反应的研究进展进行了综述,着重介绍了铑-双膦配体催化体系催化烯烃不对称加氢反应的催化机理,以及铑催化剂在烯胺、不饱和羧酸及衍生物、烯醇酯和非官能团烯烃不对称氢化中的应用,并通过对现有文献的总结指出了今后铑催化剂催化烯烃氢化反应的研究重点,即:1铑-单膦配体催化烯烃不对称氢化反应的作用机理须待提出;2非官能化底物不对称催化氢化反应的手性配体亟待拓宽。Asymmetric hydrogenation has the advantage of cleanliness,perfect atom economy,and is one of the hottest methods of asymmetric synthesis. The asymmetric hydrogenation in C=C,C=O,C=N are still primarily dependent on the use of transition metal catalysts. The study of transition metal catalysts, especially the asymmetric hydrogenation of carbon-carbon double bond catalyzed by rhodium catalysts is still an evolving field. In the present review,the progress on asymmetric hydrogenation of olefins catalyzed by rhodium catalysts are described, including the catalytic mechanism of rhodium-diphosphine ligand catalyst system, the application of asymmetric hydrogenation of enamines,unsaturated carboxylic acids and their derivatives,enol ester as well as unfunctionalized olefins catalyzed by rhodium catalysts. The development trend of rhodium catalysts for asymmetric hydrogenation of olefins was pointed out. For instance:1 the catalytic mechanism of asymmetric hydrogenation of olefins by rhodium-monophosphine ligand needs to be understood; 2 more chiral ligands for asymmetric hydrogenation of unfunctionalized olefins are still wanted.
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