廉价过渡金属催化烯烃异构反应研究进展  

Advances in Olefin Isomerization Reactions Catalyzed by the First-row Transition Metals

作　　者：吴强[1,2] 康传清[1] 高连勋[1] 

机构地区：[1]中国科学院长春应用化学研究所,高分子物理与化学国家重点实验室,长春130022 [2]中国科学院大学,北京100049

出　　处：《应用化学》2017年第1期25-39,共15页Chinese Journal of Applied Chemistry

基　　金：吉林省科技攻关项目资助(20140203003GX)~~

摘　　要：过渡金属催化的烯烃异构反应在有机化合物合成、日用化学品合成、原料油应用和天然产物合成中都有着举足轻重的作用。廉价过渡金属由于其在资源、价格、后处理等方面的优势,日益受到研究者的重视。本文主要综述了近几十年来廉价过渡金属铁、钴、镍在催化烯烃异构反应方面的研究进展,详细阐述了不同的催化体系在催化活性、反应选择性、底物适用性及反应机理方面的特点。虽然目前的催化体系已经表现出优异的性能与应用价值,但在烯烃异构的立体选择性、区域选择性机制等方面,仍然需要更深入的研究。Transition-metal-catalyzed olefin isomerization has played a crucial role in the synthesis of organic compounds,commodity chemicals,natural products,and petroleum feedstocks. Although noble metals such as Ru,Rh and Ir as catalysts for the conversions have made dramatic achievements,the disadvantages of the rare resource,high cost,and poisoning products have limited its wide application in the synthesis. Due to the abundant supply,low cost and easy removal from the final products,the first-row transition metals have attracted much attention from the chemists and have proven to be very promising with respect to the development of more sustainable catalytic system in olefin isomerizaton. This review summaried the advances in olefin isomerization catalyzed by iron,cobalt,nickel in the past years and illustrates the differences among different catalytic systems in catalytic activity,regio- and stereo-selectivity,and substrate scope. Recent developments in the olefin isomerization catalyzed by the first-row metals have proven to be very promising and effective. The reaction mechanism was discussed to have deep insight into the isomerization. The mechanism of olefin isomerization was illustrated clearly in the reported articles through intermolecular or intramolecular hydrogen shift,and the stereoselectivity and regioselectivity in different catalytic system was still worthy of further investigations. Further studies in the field to solve the challenges in high catalytic activity,stereoselectivity,and wide substrate scopes would bring the isomerization into better prospect.

关 键 词：烯烃异构 过渡金属 区域选择性 立体选择性 催化 

分 类 号：O621.3[理学—有机化学]