An Unusual Perpendicular Metallacycle Intermediate is the Origin of Branch Selectivity in the Rh(II)-Catalyzed C-H Alkylation of Aryl Sulfonamides with Vinylsilanes

Ken Yamazaki, Supriya Rej, Yusuke Ano, Naoto Chatani

Research output: Contribution to journalArticlepeer-review

Abstract

The rhodium(II)-catalyzed, branch-selective C-H alkylation of aryl sulfonamides with vinylsilanes was recently developed by our group, and the unique reactivity and selectivity of the reaction was extensively studied using density functional theory (DFT) calculations. A detailed computational study of the experimentally confirmed reaction intermediates permitted us to understand the nature of dirhodium complexes, and the findings indicated that a strained perpendicular metallacycle is formed, which disfavors the development of linear-selective migratory insertion transition states.

Original languageEnglish
Pages (from-to)3935-3942
Number of pages8
JournalOrganometallics
Volume40
Issue number23
DOIs
Publication statusPublished - Dec 13 2021
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'An Unusual Perpendicular Metallacycle Intermediate is the Origin of Branch Selectivity in the Rh(II)-Catalyzed C-H Alkylation of Aryl Sulfonamides with Vinylsilanes'. Together they form a unique fingerprint.

Cite this