Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2889-2897.DOI: 10.6023/cjoc202404018 Previous Articles     Next Articles

ARTICLES

钴催化末端烯烃区域和立体选择性异构合成反式-2-烯烃

杜佳言a,b, 刘俊涛b,c, 刘桂霞b,*(), 黄正b,c,*()   

  1. a 上海科技大学物质科学与技术学院 上海 201210
    b 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
    c 国科大杭州高等研究院化学与材料科学学院 杭州 310024
  • 收稿日期:2024-04-12 修回日期:2024-05-06 发布日期:2024-05-10
  • 通讯作者: 刘桂霞, 黄正
  • 作者简介:
    共同第一作者.
  • 基金资助:
    国家重点研发计划(2021YFA1500100); 国家自然科学基金(21825109); 国家自然科学基金(21821002); 国家自然科学基金(22072178); 国家自然科学基金(22293013); 中国科学院战略性先导科技专项(XDB0610000); 中国科学院稳定支持基础研究领域青年团队计划(YSBR-094); 上海市科学技术委员会(23JC1404400); 中科院青年交叉团队(JCTD-2021-11)

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

Jiayan Dua,b, Juntao Liub,c, Guixia Liub(), Zheng Huangb,c()   

  1. a School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032
    c School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024
  • Received:2024-04-12 Revised:2024-05-06 Published:2024-05-10
  • Contact: Guixia Liu, Zheng Huang
  • About author:
    These authors contributed equally to this work.
  • Supported by:
    National Key R&D Program of China(2021YFA1500100); National Natural Science Foundation of China(21825109); National Natural Science Foundation of China(21821002); National Natural Science Foundation of China(22072178); National Natural Science Foundation of China(22293013); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000); CAS Project for Young Scientists in Basic Research(YSBR-094); Science and Technology Commission of Shanghai Municipality(23JC1404400); CAS Youth Interdisciplinary Team(JCTD-2021-11)

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 of β-H elimination at the allylic position is likely the rate-determining step.

Key words: cobalt catalysis, alkenes, isomerization, regioselectivity, stereoselectivity