Nickel-Catalyzed Barton Decarboxylation and Giese Reactions: A Practical Take on Classic Transforms

Angew Chem Int Ed Engl. 2017 Jan 2;56(1):260-265. doi: 10.1002/anie.201609662. Epub 2016 Dec 16.

Abstract

Two named reactions of fundamental importance and paramount utility in organic synthesis have been reinvestigated, the Barton decarboxylation and Giese radical conjugate addition. N-hydroxyphthalimide (NHPI) based redox-active esters were found to be convenient starting materials for simple, thermal, Ni-catalyzed radical formation and subsequent trapping with either a hydrogen atom source (PhSiH3 ) or an electron-deficient olefin. These reactions feature operational simplicity, inexpensive reagents, and enhanced scope as evidenced by examples in the realm of peptide chemistry.

Keywords: conjugate addition; decarboxylation; esters; nickel catalysis; redox-active.

Publication types

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

MeSH terms

  • Alkenes / chemistry*
  • Catalysis
  • Decarboxylation
  • Electrons
  • Esters / chemistry*
  • Free Radicals / chemistry
  • Molecular Structure
  • Nickel / chemistry*
  • Oxidation-Reduction
  • Phthalimides / chemistry*

Substances

  • Alkenes
  • Esters
  • Free Radicals
  • Phthalimides
  • Nickel
  • N-hydroxyphthalimide