Pericyclic Cascade with Chirality Transfer: Reaction Pathway and Origin of Enantioselectivity of the Hetero-Claisen Approach to Oxindoles

Authors

  • Dr. Nihan Çelebi-Ölçüm,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
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  • Dr. Yu-hong Lam,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
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  • Edward Richmond,

    1. EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST (UK)
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  • Dr. Kenneth B. Ling,

    1. EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST (UK)
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  • Dr. Andrew D. Smith,

    Corresponding author
    1. EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST (UK)
    • EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST (UK)
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  • Prof. Dr. Dr. Kendall N. Houk

    Corresponding author
    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
    • Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
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  • We thank the UCLA IDRE, the ShaRCS Pilot Project for the UC systems, and the NCSA TeraGrid for computer time. The NIGMS-NIH (grant GM-36700 to K.N.H.), Royal Society (URF to A.D.S.), EPSRC (K.B.L.) and Cancer Research UK (E.R.) are thanked for funding.

Abstract

original image

Eine neue pericyclische Kaskade für die auxiliargesteuerte asymmetrische Synthese von 3,3-disubstituierten Oxindolen ausgehend von Nitronen und Ketenen wird vorgestellt. Die bemerkenswerte acyclische stereochemische 1,6-Induktion kann mit einer stereoselektiven 3+2-Cycloaddition und der Übertragung von Chiralität durch eine hetero-[3,3]-sigmatrope Umlagerung erklärt werden (siehe Bild; PG=Schutzgruppe).

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