Chelation-assisted carbon-carbon bond activation by Rh(I) catalysts

Chul Ho Jun, Choong Woon Moon, Hyuk Lee, Dae Yon Lee

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Abstract

Herein described is the chelation-assisted C-C bond activation of unstrained ketones under the co-catalyst system of Rh(PPh3)3Cl and 2-amino-3-picoline (1). This reaction is based on the strategy we recently developed in hydroacylation with aldehydes in which 2-aminopyridine derivatives function as chelation-assistant tools. Unstrained ketones having a β-hydrogen gave rise to alkyl-exchanged ketones via this C-C bond activation under an excess of external olefins. In the absence of external olefins, cycloheptanone underwent a ring contraction to generate five- and six-membered cyclic ketones. Instead of unstrained ketones, sec-alcohols were also employed as a substrate for this C-C bond activation via hydrogen transfer. The reaction of allylamine derivatives under [Rh(C8H14)2Cl]2 and PCy3 afforded symmetric dialkyl ketones via a series of reaction such as olefin isomerization, C-H bond activation, and C-C bond activation. The key intermediate, the imine derived from 1 was generated from a primary amine through dehydrogenation followed by transimination. Consequently, the Rh(I)-catalyzed C-C bond activation of unstrained ketones and their equivalents was demonstrated by utilizing a chelation-assistance strategy.

Original languageEnglish
Pages (from-to)145-156
Number of pages12
JournalJournal of Molecular Catalysis A: Chemical
Volume189
Issue number1
DOIs
Publication statusPublished - 2002 Oct 16

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

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