Chelation-assisted RhI-catalyzed ortho-alkylation of aromatic ketimines or ketones with olefins

Chul Ho Jun, Choong Woon Moon, Jun Bae Hong, Sung Gon Lim, Kwan Yong Chung, Yeon Hee Kim

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Abstract

Described herein is the RhI-catalyzed ortho-alkylation of aromatic ketimines or ketones with olefins. This method showed high reactivity and selectivity to monoalkylation for a variety of olefins including 1-alkenes with an allylic proton, a,w-dienes, and internal olefins. For a mechanistic study, H/D exchange experiments were carried out, which demonstrated that the ortho C-H bond could be easily cleaved even at the low temperature of 45°C. The key step of this reaction is the formation of a stable five-membered metallacycle by a chelation-assisted ortho C-H bond activation. Furthermore, the direct ortho-alkylation of aromatic ketones with the RhI complex was successfully achieved by adding 50 mol % of benzylamine as a chelation-assistant tool.

Original languageEnglish
Pages (from-to)485-492
Number of pages8
JournalChemistry - A European Journal
Volume8
Issue number2
DOIs
Publication statusPublished - 2002 Jan 18

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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