Chemoselective Primary Amination of Aryl Boronic Acids by P^III/P^V=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: radosevichmit.edu

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

DOI: 10.1021/jacs.2c02922

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Abstract

A phosphetane-based catalyst operating within P^III/P^V=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

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

T. V. Nykaza, J. C. Cooper, G. Li, N. Mahieu, A. Ramirez, M. R. Luzung, A. T. Radosevich, J. Am. Chem. Soc., 2018, 140, 15200-15205.

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

G. Li, Z. Qin, A. T. Radosevich, J. Am. Chem. Soc., 2020, 142, 16205-16210.

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.

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Key Words

anilines, organocatalysis, phenylsilane

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ID: J48-Y2022