Cobalt-Catalyzed Regio-and Stereoselective Isomerization of Terminal Alkenes to trans-2-Alkenes  

钴催化末端烯烃区域和立体选择性异构合成反式-2-烯烃

作　　者：Du Jiayan Liu Juntao Liu Guixia Huang Zheng 杜佳言;刘俊涛;刘桂霞;黄正(上海科技大学物质科学与技术学院,上海201210;中国科学院上海有机化学研究所,金属有机化学国家重点实验室,中国科学院大学,上海200032;国科大杭州高等研究院化学与材料科学学院,杭州310024)

机构地区：[1]School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210 [2]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032 [3]School of Chemistry and Materials Science,Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences,Hangzhou 310024

出　　处：《有机化学》2024年第9期2889-2897,共9页Chinese Journal of Organic Chemistry

基　　金：国家重点研发计划(No.2021YFA1500100);国家自然科学基金(Nos.21825109,21821002,22072178,22293013);中国科学院战略性先导科技专项(No.XDB0610000);中国科学院稳定支持基础研究领域青年团队计划(No.YSBR-094);上海市科学技术委员会(No.23JC1404400);中科院青年交叉团队(No.JCTD-2021-11)资助项目.

摘　　要：An efficient and E-selective monoisomerization of 1-alkenes is developed with a bis(phosphine)-based PCP-type Co complex as the catalyst.The protocol provides an atom-economical approach to trans-2-alkenes with high regio-and stereoselectivity,featuring mild conditions and wide substrate scope.Mechanistic investigation supports a cobalt-hydride pathway involving reversible alkene insertion/β-H elimination,and the step ofβ-H elimination at the allylic position is likely the rate-determining step.以双膦基PCP型钴络合物为催化剂,发展了一种高效、反式选择性的1-烯烃单异构化反应.该反应为反式-2-烯烃的合成提供了一种原子经济性方法,具有条件温和、底物范围广、区域选择性和立体选择性优异等优点.机理研究表明该异构反应可能经历Co-H反应途径,涉及可逆的烯烃插入/β-H消除,并且烯丙基位的β-H消除可能是反应的决速步.

关 键 词：cobalt catalysis ALKENES ISOMERIZATION regioselectivity STEREOSELECTIVITY 

分 类 号：TQ426[化学工程] TQ221.2