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2024 , Vol. 44 >Issue 9: 2889 - 2897

DOI: https://doi.org/10.6023/cjoc202404018

研究论文

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 ,
  • 刘俊涛 ,
  • 刘桂霞 ,
  • 黄正
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  • 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
†共同第一作者.

收稿日期: 2024-04-12

  修回日期: 2024-05-06

  网络出版日期: 2024-05-11

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)

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

  • Jiayan Du ,
  • Juntao Liu ,
  • Guixia Liu ,
  • Zheng Huang
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  • 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
†These authors contributed equally to this work.
*E-mail: ;

Received date: 2024-04-12

  Revised date: 2024-05-06

  Online published: 2024-05-11

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)

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摘要

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： 钴催化; 烯烃; 异构; 区域选择性; 立体选择性

本文引用格式

杜佳言 , 刘俊涛 , 刘桂霞 , 黄正 . 钴催化末端烯烃区域和立体选择性异构合成反式-2-烯烃[J]. 有机化学, 2024 , 44(9) : 2889 -2897 . DOI: 10.6023/cjoc202404018

Abstract

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

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