Organic Carbonates as Alternative Solvents for Palladium-Catalyzed Substitution Reactions

Authors

  • Benjamin Schäffner,

    1. Leibniz Institut für Katalyse e.V., Universität Rostock, Albert-Einstein Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381-1281-5202
    Search for more papers by this author
  • Jens Holz Dr.,

    1. Leibniz Institut für Katalyse e.V., Universität Rostock, Albert-Einstein Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381-1281-5202
    Search for more papers by this author
  • Sergey P. Verevkin,

    1. Institut für Chemie der Universität Rostock, Albert-Einstein Strasse 3a, 18059 Rostock, Germany
    Search for more papers by this author
  • Armin Börner Prof. Dr.

    1. Leibniz Institut für Katalyse e.V., Universität Rostock, Albert-Einstein Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381-1281-5202
    2. Institut für Chemie der Universität Rostock, Albert-Einstein Strasse 3a, 18059 Rostock, Germany
    Search for more papers by this author

Abstract

Organic carbonates, such as propylene carbonate, butylene carbonate, and diethyl carbonate, were tested in the Pd-catalyzed asymmetric allylic substitution reactions of rac-1,3-diphenyl-3-acetoxy-prop-1-ene with dimethyl malonate or benzylamine as nucleophiles. Bidentate diphosphanes were used as chiral ligands. The application of monodentate phosphanes capable of self-assembling with the metal was likewise tested. In the substitution reaction with dimethyl malonate, enantioselectivities up to 98 % were achieved. In the amination reaction, the chiral product was obtained with up to 83 % ee. The results confirm that these “green solvents” can be advantageously used for this catalytic transformation as an alternative to those solvents usually employed which run some risk of being harmful to the environment.

Ancillary