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Activator-Free Olefin Oligomerization and Isomerization Reactions Catalyzed by an Air- and Water-Tolerant Wacker Oxidation Intermediate

Authors

  • Matthew S. Winston,

    1. Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (USA)
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  • Paul F. Oblad,

    1. Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (USA)
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  • Dr. Jay A. Labinger,

    Corresponding author
    1. Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (USA)
    • Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (USA)
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  • Prof. John E. Bercaw

    Corresponding author
    1. Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (USA)
    • Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (USA)
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  • This work was supported by BP. We thank Dr. Glenn Sunley (BP) for helpful discussions, and Dr. Loi Do and Larry Henling for X-ray crystallographic analysis.

Abstract

original image

A bench-stable, hydroxy-bridged α-diimine-Pd dimer can self-activate to an olefin oligomerization and isomerization catalyst in the presence of substrate (see scheme). A cationic Pd-hydride is generated principally through a Wacker oxidation of olefin to ketone, and with C4+ olefins, lesser amounts of allylic C-H activation, β-H transfer, and release of diene products are observed.

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