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

Research output: Contribution to journalArticle

90 Citations (Scopus)

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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Alkylation
Alkenes
Chelation
Ketones
Olefins
Protons
Chemical activation
ketimine
Experiments
Temperature

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Jun, Chul-Ho ; Moon, Choong Woon ; Hong, Jun Bae ; Lim, Sung Gon ; Chung, Kwan Yong ; Kim, Yeon Hee. / Chelation-assisted RhI-catalyzed ortho-alkylation of aromatic ketimines or ketones with olefins. In: Chemistry - A European Journal. 2002 ; Vol. 8, No. 2. pp. 485-492.
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Chelation-assisted RhI-catalyzed ortho-alkylation of aromatic ketimines or ketones with olefins. / Jun, Chul-Ho; Moon, Choong Woon; Hong, Jun Bae; Lim, Sung Gon; Chung, Kwan Yong; Kim, Yeon Hee.

In: Chemistry - A European Journal, Vol. 8, No. 2, 18.01.2002, p. 485-492.

Research output: Contribution to journalArticle

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