铑（I）催化烯基亚乙烯基环丙烷的二聚反应用于构建螺[4,5]癸烷及机理研究

Rh(i)-catalyzed dimerization of ene-vinylidenecyclopropanes for the construction of spiro[4,5]decanes and mechanistic studies.

作者信息

Ning Chao, Rui Kang-Hua, Wei Yin, Shi Min

机构信息

Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Key Laboratory for Advanced Materials, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry & Molecular Engineering, East China University of Science and Technology Meilong Road No. 130 Shanghai 200237 China

State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, University of Chinese Academy of Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China

出版信息

Chem Sci. 2022 Jun 1;13(24):7310-7317. doi: 10.1039/d1sc06986a. eCollection 2022 Jun 22.

Rh(i) complex catalyzed dimerization of ene-vinylidenecyclopropanes took place smoothly to construct a series of products containing spiro[4,5]decane skeletons featuring a simple operation procedure, mild reaction conditions, and good functional group tolerance. In this paper, the combination of experimental and computational studies reveals a counterion-assisted Rh(i)-Rh(iii)-Rh(v)-Rh(iii)-Rh(i) catalytic cycle involving tandem oxidative cyclometallation/reductive elimination/selective oxidative addition/selective reductive elimination/reductive elimination steps; in addition, a pentavalent spiro-rhodium intermediate is identified as the key intermediate in this dimerization reaction upon DFT calculation.