A Concerted Transfer Hydrogenolysis: 1,3,2-Diazaphospholene-Catalyzed Hydrogenation of N[DOUBLE BOND]N Bond with Ammonia–Borane

Authors

  • Che Chang Chong,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21,Singapore 637371 (Singapore)
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  • Prof. Dr. Hajime Hirao,

    Corresponding author
    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21,Singapore 637371 (Singapore)
    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21,Singapore 637371 (Singapore)===

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  • Prof. Dr. Rei Kinjo

    Corresponding author
    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21,Singapore 637371 (Singapore)
    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21,Singapore 637371 (Singapore)===

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  • We are grateful to Nanyang Technological University and the Singapore Ministry of Education (MOE2013-T2-1-005) for financial support, and Dr. Rakesh Ganguly and Dr. Yongxin Li (Nanyang Technological University) for assistance in X-ray crystallographic analysis.

Abstract

1,3,2-diazaphospholenes catalyze metal-free transfer hydrogenation of a N[DOUBLE BOND]N double bond using ammonia–borane under mild reaction conditions, thus allowing access to various hydrazine derivatives. Kinetic and computational studies revealed that the rate-determining step involves simultaneous breakage of the B[BOND]H and N[BOND]H bonds of ammonia–borane. The reaction is therefore viewed as a concerted type of hydrogenolysis.

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