Mechanism Selection for Regiocontrol in Base-Assisted, Palladium-Catalysed Direct C[BOND]H Coupling with Halides: First Approach for Oxazole- and Thiazole-4-Carboxylates

Authors

  • Laure Théveau,

    1. Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    Search for more papers by this author
  • Dr. Cécile Verrier,

    1. Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    Search for more papers by this author
  • Pierrik Lassalas,

    1. Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    Search for more papers by this author
  • Dr. Thibaut Martin,

    1. Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    Search for more papers by this author
  • Prof. Dr. Georges Dupas,

    1. Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    Search for more papers by this author
  • Dr. Olivier Querolle,

    1. JANSSEN Research and Development, Medicinal Chemistry Department, Campus de Maigremont, BP 615 27106 Val de Reuil Cedex (France)
    Search for more papers by this author
  • Dr. Luc Van Hijfte,

    1. JANSSEN Research and Development, Medicinal Chemistry Department, Campus de Maigremont, BP 615 27106 Val de Reuil Cedex (France)
    Search for more papers by this author
  • Prof. Dr. Francis Marsais,

    1. Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    Search for more papers by this author
  • Dr. Christophe Hoarau

    Corresponding author
    1. Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    • Institut de Chimie Organique Fine associé au CNRS (UMR 6014), INSA et Université de Rouen, Place Emile Blondel, BP 08 76131 Mont Saint Aignan (France), Fax: (+33) 235522469
    Search for more papers by this author

Errata

This article is corrected by:

  1. Errata: Corrigendum: Mechanism Selection for Regiocontrol in Base-Assisted, Palladium-Catalysed Direct C[BOND]H Coupling with Halides: First Approach for Oxazole- and Thiazole-4-Carboxylates Volume 18, Issue 7, 1857, Article first published online: 3 February 2012

Abstract

Both base-assisted non-concerted metallation–deprotonation (nCMD) and concerted metallation–deprotonation (CMD) have been identified as two potent operating mechanisms in palladium-catalysed direct C[BOND]H coupling of oxazole and thiazole-4-carboxylate esters with halides through base- and solvent-effect experiments. Novel C2- and C5-selective CMD direct arylation procedures in oxazole- and thiazole-4-carboxylate series were then designed by controlling the balance between electronic and steric factors. Notably, charge interactions between the palladium catalyst and substrate were identified as a parameter for controlling selectivity and reducing the impact of steric factors in the CMD reaction.

Ancillary