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

ABSTRACT: 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.

SUBMITTER: Ning C

PROVIDER: S-EPMC9214856 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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

Ning Chao C Rui Kang-Hua KH Wei Yin Y Shi Min M

Chemical science 20220601 24

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 oxidativ ...[more]

PMID: 35799819

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