A Study of the Heck Reaction in Non-Polar Hydrocarbon Solvents and in Supercritical Carbon Dioxide

Jin-Kyun Lee; Rachel M. Williamson; Andrew B. Holmes; Edward J. Bush; Ian F. McConvey

doi:10.1071/CH07160

RESEARCH ARTICLE

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A Study of the Heck Reaction in Non-Polar Hydrocarbon Solvents and in Supercritical Carbon Dioxide

Jin-Kyun Lee ^A ^B , Rachel M. Williamson ^C , Andrew B. Holmes ^A ^C ^E , Edward J. Bush ^D and Ian F. McConvey ^D

+ Author Affiliations

- Author Affiliations

^A Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.

^B Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA.

^C School of Chemistry, Bio21 Institute, University of Melbourne, VIC 3010, Australia.

^D Process R&D, AstraZeneca Pharmaceuticals, Silk Road Business Park, Macclesfield, Cheshire SK10 2NA, UK.

^E Corresponding author. Email: aholmes@unimelb.edu.au

Australian Journal of Chemistry 60(8) 566-571 https://doi.org/10.1071/CH07160
Submitted: 18 May 2007 Accepted: 28 June 2007 Published: 9 August 2007

Abstract

The effects of electronic and steric properties of phosphorus ligands on Heck reactions in supercritical CO₂ and non-polar hydrocarbon solvents were studied. In Heck reactions between iodobenzene and butyl acrylate, higher yields were obtained with less electron-rich phosphine ligands. This trend was also observed with the electron-poor triphenyl phosphite. A range of sterically demanding phosphites were then investigated. Biphenyl-containing phosphites 8 and 13 were found to be highly effective. In the Heck reaction between the less-reactive bromobenzene and butyl acrylate, the bulky, electron-rich tri-tert-butylphosphine ligand produced the best yield. These results emphasize the importance of both electronic and steric properties of phosphorus ligands in the Heck reaction in non-polar solvents.

Acknowledgments

We thank AstraZeneca (UK), the Overseas Research Students Awards Scheme (Universities UK), the Cambridge Overseas Trust, the Engineering and Physical Sciences Research Council (UK), the Australian Research Council, VESKI, and CSIRO for generous financial support. This project was carried out with partial support from the Materials World Network (NSF/ARC). We thank Dr C. J. Smith, Dr M. W. S. Tsang, and Dr D. J. Jones for their interest in this work. We also thank Dr U. Wille for assistance with GC analyses.

References

A Study of the Heck Reaction in Non-Polar Hydrocarbon Solvents and in Supercritical Carbon Dioxide

Abstract

Acknowledgments

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