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Amide Synthesis by Nucleophilic Attack of Vinyl Azides†

Authors

  • Feng-Lian Zhang,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
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  • Dr. Yi-Feng Wang,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
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  • Geoffroy Hervé Lonca,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
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  • Xu Zhu,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
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  • Prof. Shunsuke Chiba

    Corresponding author
    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)

    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)

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  • †

    This work was supported by funding from Nanyang Technological University and the Singapore Ministry of Education. Y.-F.W. is thankful for a Lee Kuan Yew postdoctoral fellowship (the LKY PDF). G.H.L. is grateful for financial support from the Ecole Polytechnique.

Abstract

A method for the synthesis of amide-containing molecules was developed using vinyl azides as an enamine-type nucleophile towards carbon electrophiles, such as imines, aldehydes, and carbocations that were generated from alcohols in the presence of BF3⋅OEt2. After nucleophilic attack of the vinyl azide, a substituent of the resulting iminodiazonium ion intermediate migrates to form a nitrilium ion, which is hydrolyzed to afford the corresponding amide.

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Article Information

DOI

10.1002/anie.201400938

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© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Keywords

  • amides;
  • nitrilium ions;
  • nucleophilic attack;
  • rearrangement;
  • vinyl azides

Publication History

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  • Manuscript Received:

Funded by

  • Nanyang Technological University
  • Singapore Ministry of Education
  • Ecole Polytechnique

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