Enantioselective Allylic C-H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis

Angew Chem Int Ed Engl. 2016 Aug 8;55(33):9571-5. doi: 10.1002/anie.201603576. Epub 2016 Jul 4.

Abstract

The enantioselective synthesis of isochroman motifs has been accomplished by palladium(II)-catalyzed allylic C-H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C-H oxidation reaction proceeds with the broadest scope and highest levels of asymmetric induction reported to date (avg. 92 % ee, 13 examples with greater than 90 % ee).

Keywords: C−H activation; S ligands; asymmetric catalysis; oxidation; palladium.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Alkenes / chemistry*
  • Allyl Compounds / chemistry*
  • Catalysis
  • Chromans / chemical synthesis*
  • Chromans / chemistry
  • Molecular Structure
  • Oxidation-Reduction
  • Palladium / chemistry*
  • Stereoisomerism
  • Sulfoxides / chemistry*

Substances

  • Alkenes
  • Allyl Compounds
  • Chromans
  • Sulfoxides
  • Palladium