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Copper-Catalyzed Cyclization/aza-Claisen Rearrangement Cascade Initiated by Ketenimine Formation: An Efficient Stereocontrolled Synthesis of α-Allyl Cyclic Amidines

Authors

  • Dr. Hua-Dong Xu,

    Corresponding author
    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
    • School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)

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  • Zhi-Hong Jia,

    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
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    • These authors contributed equally to this work.

  • Ke Xu,

    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
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    • These authors contributed equally to this work.

  • Mei Han,

    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
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  • Sai-Nan Jiang,

    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
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  • Jing Cao,

    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
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  • Jia-Cheng Wang,

    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
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  • Dr. Mei-Hua Shen

    Corresponding author
    1. School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)
    • School of Pharmaceutical Engineering and Life Science, Changzhou University, First Middle Gehu Road, Changzhou, Jiangsu Province, 213164 (China)

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  • This work was supported by the Natural Science Foundation of China (21002032 and 21272077), Shanghai Pujiang Program (11J1403100), Priority Academic Program Development of Jiangsu High Education Institutions (PAPD), and the Natural Science Foundation of Jiangsu Province (SBK201321632). We are grateful to Prof. Yang Yang at the Instrument Analysis Center of CCZU for his generous help with the NOSEY analysis.

Abstract

An efficient and convenient synthesis of α-allyl cyclic amidines has been achieved by applying a novel cascade reaction. Copper(I)-mediated in situ N-sulfonyl ketenimine formation from the reaction of a terminal alkyne with sulfonyl azide is followed by an intramolecular nucleophilic attack on the central carbon atom by an allylic tertiary amine, and then an aza-Claisen rearrangement takes place through a chair transition state to furnish the titled amidines with complete stereocontrol.

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