Evidence for spontaneous release of acrylates from a transition-metal complex upon coupling ethene or propene with a carboxylic moiety or CO(2)

Chemistry. 2007;13(32):9028-34. doi: 10.1002/chem.200700532.

Abstract

The development of a new synthetic approach to acrylates based on the formation of alkyl esters of acrylic acids has been studied. A preformed Pd-COOMe moiety is used as a model system to investigate the insertion of an olefin into the Pd--C bond. The fast elimination of acrylate is observed. Density functional calculations support the experimental findings and allow the characterization of transition states along the reaction pathway. The first example of olefin/CO(2) coupling with facile release of ethyl acrylate is also presented.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrylates / chemical synthesis*
  • Acrylates / chemistry
  • Alkenes / chemistry*
  • Carbon Dioxide / chemistry*
  • Carboxylic Acids / chemistry*
  • Ethylenes / chemistry*
  • Models, Chemical
  • Molecular Conformation
  • Organometallic Compounds / chemistry*
  • Stereoisomerism
  • Transition Elements / chemistry

Substances

  • Acrylates
  • Alkenes
  • Carboxylic Acids
  • Ethylenes
  • Organometallic Compounds
  • Transition Elements
  • Carbon Dioxide
  • ethylene
  • propylene