Palladium(0)-catalyzed intramolecular decarboxylative allylation of ortho nitrobenzoic esters

Org Lett. 2014 Aug 1;16(15):3934-7. doi: 10.1021/ol5017349. Epub 2014 Jul 23.

Abstract

A Pd/Ag bimetallic system has been developed for the decarboxylative allylation of ortho-nitrobenzoic esters in an intramolecular fashion. In contrast to the typical sp(2)-sp(3) cross-coupling approach which requires air and moisture sensitive preformed organometallic reagents, we provide an alternative route to the synthesis of ortho-allyl nitroarenes from the corresponding ortho-nitrobenzoic acid derivatives. The reaction proceeds through a mechanistically distinct decarboxylative metalation pathway. A cooperative reactivity of palladium and silver is crucial for the reaction outcome.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Allyl Compounds / chemical synthesis*
  • Allyl Compounds / chemistry
  • Catalysis
  • Esters
  • Molecular Structure
  • Nitrobenzoates / chemical synthesis*
  • Nitrobenzoates / chemistry*
  • Palladium / chemistry*
  • Stereoisomerism

Substances

  • Allyl Compounds
  • Esters
  • Nitrobenzoates
  • Palladium