Enantioselective oxidative gold catalysis enabled by a designed chiral P,N-bidentate ligand

Angew Chem Int Ed Engl. 2015 Jan 19;54(4):1245-9. doi: 10.1002/anie.201409300. Epub 2014 Nov 27.

Abstract

A newly developed P,N-bidentate ligand enables enantioselective intramolecular cyclopropanation by a reactive α-oxo gold carbene intermediate generated in situ. The ligand design is based on our previously proposed structure (with a well-organized triscoordinated gold center) of the carbene intermediate in the presence of a P,N-bidentate ligand. A C2-symmetric piperidine ring was incorporated in the ligand as the nitrogen-containing moiety. A range of racemic transformations of α-oxo gold carbene intermediates have been developed recently, and this new class of chiral ligands could enable their modification for asymmetric synthesis, as demonstrated in this study.

Keywords: asymmetric catalysis; carbenes; cyclopropanation; gold; oxidation.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Catalysis
  • Crystallography, X-Ray
  • Cyclopropanes / chemistry
  • Gold / chemistry*
  • Ligands*
  • Methane / analogs & derivatives
  • Methane / chemistry
  • Molecular Conformation
  • Nitrogen / chemistry
  • Oxidation-Reduction
  • Phosphorus / chemistry
  • Piperidines / chemistry
  • Stereoisomerism

Substances

  • Cyclopropanes
  • Ligands
  • Piperidines
  • carbene
  • Phosphorus
  • piperidine
  • Gold
  • cyclopropane
  • Nitrogen
  • Methane