Cobalt/Salox-Catalyzed Enantioselective C-H Functionalization of Arylphosphinamides

Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202202892. doi: 10.1002/anie.202202892. Epub 2022 Apr 21.

Abstract

Previous methods on CoIII -catalyzed asymmetric C-H activation rely on the use of tailor-made cyclopentadienyl-ligated CoIII complexes, which require lengthy steps for the preparation. Herein, we report an unprecedented enantioselective C-H functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and chiral amino alcohols. A broad range of P-stereogenic compounds were synthesized in high yields with excellent enantioselectivities (45 examples, up to 99 % yield and >99 % ee). The isolation and characterization of several intermediates provided insights into the generation of active catalytic cobalt species, the action of Salox, and the mode of stereocontrol.

Keywords: Annulation; Cobalt; C−H Activation; Enantioselectivity; Salicyloxazoline.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Cobalt*
  • Ligands
  • Molecular Structure
  • Stereoisomerism

Substances

  • Ligands
  • Cobalt