Inorganic-Base-Mediated Hydroamination of Alkenyl Oximes for the Synthesis of Cyclic Nitrones

Authors

  • Dr. Xingao Peng,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
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  • Benny Meng Kiat Tong,

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

    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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  • 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 (Academic Research Fund Tier 2: MOE2012-T2-1-014).

Abstract

A method based on hydroamination mediated by inorganic base was developed for the synthesis of cyclic nitrones from alkenyl oximes. DFT calculations of the reaction pathway suggested that this hydroamination could proceed through an unprecedented nucleophilic amination of the unactivated alkene by the oxime nitrogen atom. The transition state of this reaction is stabilized by an ionic interaction between a metal cation such as K+ and the oxime oxygen and negatively charged alkene moiety.

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