Catalytic ketyl-olefin cyclizations enabled by proton-coupled electron transfer

J Am Chem Soc. 2013 Jul 10;135(27):10022-5. doi: 10.1021/ja404342j. Epub 2013 Jun 28.

Abstract

Concerted proton-coupled electron transfer is a key mechanism of substrate activation in biological redox catalysis. However, its applications in organic synthesis remain largely unexplored. Herein, we report the development of a new catalytic protocol for ketyl-olefin coupling and present evidence to support concerted proton-coupled electron transfer being the operative mechanism of ketyl formation. Notably, reaction outcomes were correctly predicted by a simple thermodynamic formalism relating the oxidation potentials and pKa values of specific Brønsted acid/reductant combinations to their capacity to act jointly as a formal hydrogen atom donor.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes / chemistry*
  • Catalysis
  • Cyclization
  • Electrons
  • Ketones / chemical synthesis*
  • Ketones / chemistry*
  • Molecular Structure
  • Oxidation-Reduction
  • Protons
  • Thermodynamics

Substances

  • Alkenes
  • Ketones
  • Protons