Computational Characterization of a Complete Palladium-Catalyzed Cross-Coupling Process:  The Associative Transmetalation in the Stille Reaction

Rosana Álvarez,* Olalla Nieto Faza, Carlos Silva López, and Ángel R. de Lera*;
Departamento de Qumica Orgnica, Universidade de Vigo, Lagoas-Marcosende 36310 Vigo, Spain
Org. Lett., 2006, 8 (1), pp 35–38
DOI: 10.1021/ol052398f
Publication Date (Web): December 9, 2005
Copyright © 2006 American Chemical Society
*

 Fax:  34 986811940. Phone:  34 986812316.

, rar@uvigo.es, ; , qolera@uvigo.es

Abstract

Abstract Image

The species presumably involved in the associative ligand substitution mechanism for the Stille cross coupling of vinyl bromide and trimethylvinyl stannane with Pd(PMe3)2/PMe3 as catalysts in DMF (as ligand and solvent) have been structurally and energetically characterized. The cyclic four-coordinate transition state for the rate-determining transmetalation step explains the retention of configuration in the Stille coupling of chiral nonracemic alkyl stannanes.

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History

  • Published In Issue January 05, 2006
  • Received October 4, 2005

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