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

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

Research output: Contribution to journalArticle

42 Citations (Scopus)

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

Fingerprint

chelation
Chelation
Ketones
ketones
Carbon
Chemical activation
activation
catalysts
Catalysts
carbon
Alkenes
alkenes
Olefins
Hydrogen
Picolines
Allylamine
Derivatives
Imines
hydrogen
Dehydrogenation

All Science Journal Classification (ASJC) codes

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

Cite this

Jun, Chul Ho ; Moon, Choong Woon ; Lee, Hyuk ; Lee, Dae Yon. / Chelation-assisted carbon-carbon bond activation by Rh(I) catalysts. In: Journal of Molecular Catalysis A: Chemical. 2002 ; Vol. 189, No. 1. pp. 145-156.
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Chelation-assisted carbon-carbon bond activation by Rh(I) catalysts. / Jun, Chul Ho; Moon, Choong Woon; Lee, Hyuk; Lee, Dae Yon.

In: Journal of Molecular Catalysis A: Chemical, Vol. 189, No. 1, 16.10.2002, p. 145-156.

Research output: Contribution to journalArticle

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AB - 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.

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