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Palladium Enolate Umpolung: Cyclative Diacetoxylation of Alkynyl Cyclohexadienones Promoted by a Pd/SPRIX Catalyst

Authors

  • Dr. Kazuhiro Takenaka,

    1. The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047 (Japan)
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  • Dr. Suman C. Mohanta,

    1. The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047 (Japan)
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  • Prof. Dr. Hiroaki Sasai

    Corresponding author
    1. The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047 (Japan)
    • The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047 (Japan)===

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  • This work was supported by the Advanced Catalytic Transformation program for Carbon utilization (ACT-C), Core Research for Evolutionary Science and Technology (CREST), a Grant-in-Aid for Scientific Research from MEXT, and the JSPS Japanese-German Graduate Externship. We would like to thank the technical staff of the ISIR Comprehensive Analysis Centre at Osaka University for their assistance. SPRIX=spiro-bis(isoxazoline).

Abstract

A novel palladium-catalyzed reaction involving an unusual nucleophilic attack on a palladium enolate was developed using a spiro-bis(isoxazoline) (SPRIX) ligand. Treatment of alkynyl cyclohexadienone substrates with a Pd/SPRIX catalyst in acetic acid under an oxygen atmosphere furnished diacetoxylated benzofuranone derivatives in good yields. This cyclative diacetoxylation proceeded enantioselectively in the presence of an optically pure SPRIX ligand.

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