Enantiodivergent and γ-Selective Asymmetric Allylic Amination

Authors

  • Jianmin Wang,

    1. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore)
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    • These authors contributed equally to this work.

  • Jie Chen,

    1. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore)
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    • These authors contributed equally to this work.

  • Choon Wee Kee,

    1. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore)
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    • These authors contributed equally to this work.

  • Prof. Dr. Choon-Hong Tan

    Corresponding author
    1. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore)
    • Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore)
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  • This work was supported by ARF grant R-143-000-461-112 and scholarships (to J.M. and C.W.K) from the National University of Singapore.

Abstract

original image

Double agent: The title reaction using the guanidine catalyst 1 can deliver both enantiomers of the product with excellent enantioselectivity by judicious choice of the double bond geometry of the the β,γ-unsaturated carbonyl compound. Computational studies reveal the possible origin of the inversed enantioselectivity, and the potential for enantiodivergent synthesis chiral amine-containing substrates is attractive.

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