Mercury(II)- and Palladium(II)-Catalyzed [3,3]-Sigmatropic Rearrangements [New Synthetic Methods (46)]

Authors

  • Prof. Larry E. Overman

    Corresponding author
    1. Department of Chemistry, University of California, Irvine, CA 92 717 (USA)
    • Department of Chemistry, University of California, Irvine, CA 92 717 (USA)
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Abstract

Mercury(II) and palladium(II) salts have found broad applications as catalysts for [3,3]-sigmatropic rearrangements leading to formation of C[BOND]O, C[BOND]N, C[BOND]S, and C[BOND]C σ bonds. Increases in reaction rate are often very large (1010 – 1014 at 1 M catalyst concentration) and allow many previously difficult transformations to be conducted at or near room temperature, often with attendant increases in stereoselectivity and decreases in by-product formation. The mechanism of these catalyzed transformations is briefly discussed, and evidence is summarized to suggest that many follow a cyclization-induced rearrangement mechanism.

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