Theoretical Studies on Diastereo- and Enantioselective Rhodium-Catalyzed Cyclization of Diazo Compound via Intramolecular C-H Bond Insertion

Naohiko Yoshikai, Eiichi Nakamura

Research output: Contribution to journalArticlepeer-review

58 Citations (Scopus)

Abstract

Theoretical studies on the stereoselectivity of the dirhodium tetracarboxylate (carboxamidate)-catalyzed intramolecular C-H insertion reaction, which gives a variety of carbo- or heterocyclic compounds, have been performed by the following procedure. First, the C-H insertion mechanism of simple systems was studied by the hybrid density functional theory (B3LYP) calculations. On the basis of these B3LYP structures, stereoselectivities of the reactions of realistic substrates were examined by the PM3 calculations with some structural constraints. The origin of the diastereo- and enantioselectivities in the four- and five-membered ring formation reactions with an achiral or a chiral Rh catalyst has thus been elucidated.

Original languageEnglish
Pages (from-to)1159-1171
Number of pages13
JournalAdvanced Synthesis and Catalysis
Volume345
Issue number9-10
DOIs
Publication statusPublished - 2003 Sep
Externally publishedYes

Keywords

  • C-H activation
  • Carbene complex
  • Cyclization
  • Diazo compounds
  • Rhodium
  • Stereoselectivity
  • Theoretical calculation

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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