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Palladium-Catalyzed Carbocyclization of Alkynyl Ketones Proceeding through a Carbopalladation Pathway

Authors

  • Natalia Chernyak,

    1. Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor St., Rm 4500 SES, Chicago, IL 60607 (USA), Fax: (+1) 312-355-0836
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  • Dr. Serge I. Gorelsky,

    Corresponding author
    1. Centre for Catalysis Research and Innovation (CCRI), Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, ON K1N 6N5 (Canada)
    • Centre for Catalysis Research and Innovation (CCRI), Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, ON K1N 6N5 (Canada)
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  • Prof. Vladimir Gevorgyan

    Corresponding author
    1. Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor St., Rm 4500 SES, Chicago, IL 60607 (USA), Fax: (+1) 312-355-0836
    • Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor St., Rm 4500 SES, Chicago, IL 60607 (USA), Fax: (+1) 312-355-0836
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  • The support of the NIH (GM-64444) and the NSF (CHE-0710749) of US, and CCRI of Canada is gratefully acknowledged.

Abstract

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Dig this: 5-exo-dig carbocyclization of 1 into 2 features intramolecular carbopalladation of alkyne with Pd enolate (see scheme). DFT calculations show that the key Pd enolate forms by deprotonation assisted byb PdII acetate. Subsequent intramolecular alkyne carbopalladation, Z–E isomerization of the formed vinyl palladium species, and protiodepalladation leads to E-alkylidene indanones.

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