Bifunctional transition metal-based molecular catalysts for asymmetric C - C and C - N bond formation

Takao Ikariya, Ilya D. Gridnev

Research output: Contribution to journalArticle

56 Citations (Scopus)

Abstract

This paper describes die recent advances in the conceptually new bifunctional Ir and Ru catalysts for asymmetric catalytic reactions. These reactions include die enantioselective Michael addition of 1,3-dicarbonyl compounds to cyclic enones and nitroalkenes, and the enantioselective direct amination of α-cyanoacetates with diazoesters. The outcome of these reactions in terms of reactivity and selectivity was delicately influenced by the catalyst structures and the reaction conditions including the solvents used. Even with a 1 :1 molar ratio of donors to acceptors, the reactions proceeded smoothly to give the corresponding chiral adducts with an excellent yield and enantiomeric excess (ee). Preliminary mechanistic studies showed that the key stage of the catalytic cycle is the interaction of the bifunctional catalyst with a pronucleophilic reagent that leads to stereoselective formation of C-, O-, or N-bound complexes. The resulting protonated catalyst bearing metal-bound nucleophiles readily reacts widi electrophiles to provide C-C and C-N bond formation products in a highly stereoselective manner.

Original languageEnglish
Pages (from-to)106-123
Number of pages18
JournalChemical Record
Volume9
Issue number2
DOIs
Publication statusPublished - 2009 Apr 6
Externally publishedYes

Keywords

  • Asymmetric catalysis
  • Bifunctional Ir complexes
  • Bifunctional Ru complexes
  • Michael addition

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry
  • Chemical Engineering(all)
  • Materials Chemistry

Fingerprint Dive into the research topics of 'Bifunctional transition metal-based molecular catalysts for asymmetric C - C and C - N bond formation'. Together they form a unique fingerprint.

  • Cite this