Terminal olefins to chromans, isochromans, and pyrans via allylic C-H oxidation

J Am Chem Soc. 2014 Aug 6;136(31):10834-7. doi: 10.1021/ja503322e. Epub 2014 Jul 16.

Abstract

The synthesis of chroman, isochroman, and pyran motifs has been accomplished via a combination of Pd(II)/bis-sulfoxide C-H activation and Lewis acid co-catalysis. A wide range of alcohols are found to be competent nucleophiles for the transformation under uniform conditions (catalyst, solvent, temperature). Mechanistic studies suggest that the reaction proceeds via initial C-H activation followed by a novel inner-sphere functionalization pathway. Consistent with this, the reaction shows reactivity trends orthogonal to those of traditional Pd(0)-catalyzed allylic substitutions.

Publication types

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

MeSH terms

  • Alkenes / chemistry*
  • Catalysis
  • Chromans / chemistry*
  • Oxidation-Reduction
  • Palladium / chemistry
  • Pyrans / chemistry*

Substances

  • Alkenes
  • Chromans
  • Pyrans
  • Palladium