P^III/P^V=O-Catalyzed Intermolecular N-N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines

Gen Li, Steven P. Miller and Alexander T. Radosevich*

*Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States, Email: radosevichmit.edu

G. Li, S. P. Miller, A. T. Radosevich, J. Am. Chem. Soc., 2021, 143, 14464-14469.

DOI: 10.1021/jacs.1c07272

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Abstract

A small ring phosphacycle (phosphetane) catalyzes the synthesis of unsymmetrical hydrazines by cross-selective intermolecular NN reductive coupling of nitroarenes and anilines in the presence of a hydrosilane as the terminal reductant. The reaction offers good chemoselectivity and functional group tolerance.

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proposed mechanism

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A Biphilic Phosphetane Catalyzes N-N Bond-Forming Cadogan Heterocyclization via P^III/P^V=O Redox Cycling

T. V. Nykaza, T. S. Harrison, A. Ghosh, R. A. Putnik, A. T. Radosevich, J. Am. Chem. Soc., 2017, 139, 6839-6842.

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Key Words

hydrazines, diphenylsilane, organocatalysis

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ID: J48-Y2021