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Chemoselective Primary Amination of Aryl Boronic Acids by PIII/PV=O-Catalysis: Synthetic Capture of the Transient Nef Intermediate HNO

Seung Youn Hong and Alexander T. Radosevich*

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

S. Y. Hong, A. T. Radosevich, J. Am. Chem. Soc., 2022, 144, 8902-8907.

DOI: 10.1021/jacs.2c02922

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A phosphetane-based catalyst operating within PIII/PV=O redox cycling is able to capture HNO, generated in situ by Nef decomposition of 2-nitropropane, to selectively furnish versatile primary arylamines from arylboronic acid substrates with the preservation of otherwise reactive functional groups.

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proposed mechanism

Intermolecular Reductive C-N Cross Coupling of Nitroarenes and Boronic Acids by PIII/PV=O Catalysis

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P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C-N Coupling with Nitromethane as a Methylamine Surrogate

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Enabling Reductive C-N Cross-Coupling of Nitroalkanes and Boronic Acids by Steric Design of P(III)/P(V)=O Catalysts

G. Li, Y. Kanda, S. Y. Hong, A. T. Radosevich, J. Am. Chem. Soc., 2022, 144, 8242-8248.

Key Words

anilines, organocatalysis, phenylsilane

ID: J48-Y2022