Z-Selective Semihydrogenation of Alkynes Catalyzed by a Cationic Vanadium Bisimido Complex

Authors

  • Henry S. La Pierre,

    1. Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504
    Search for more papers by this author
  • Prof. Dr. John Arnold,

    Corresponding author
    1. Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504
    • Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504===

    Search for more papers by this author
  • Prof. Dr. F. Dean Toste

    Corresponding author
    1. Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504
    • Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504===

    Search for more papers by this author

  • The NIH GMS (R01 GM074774) and NSF (CHE 0848931) are gratefully acknowledged for financial support. We thank Drs. A. Pasquale, C. Canlas, and J. Krinsky for experimental assistance, Profs. R. G. Bergman and S. B. Duckett for helpful discussions, and Prof. A. Pines for a donation of para-H2. H.S.La.P. is grateful to the NSF for a pre-doctoral fellowship and the UCB Department of Chemistry for the Dauben Fellowship.

Abstract

original image

Der frühe Komplex fängt das H: Unter 1 atm H2 katalysiert der Vanadiumkomplex 1 die Semihydrierung von Alkinen zu Z-Alkenen. Synthese- und DFT-Studien in Kombination mit H2/D2- und NMR-Experimenten ergeben, dass H2 durch 1,2-Addition an 1 aktiviert wird. Nach Insertion des Alkins in die V-H-Bindung von A führt die 1,2-α-NH-Eliminierung im Alkenylliganden unter Regenerierung von 1 zum Alken.

Ancillary