Organic Chemistry Portal

Abstracts

Search:

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

Trevor V. Nykaza, Julian C. Cooper, Gen Li, Nolwenn Mahieu, Antonio Ramirez, Michael R. Luzung*, Alexander T. Radosevich*

*Bristol-Myers Squibb Company, One Squibb Drive, New Brunswick, New Jersey 08903; Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States, Email: mikekallyope.com, radosevichmit.edu

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.

DOI: 10.1021/jacs.8b10769


see article for more reactions

Abstract

A transition-metal-free synthesis of aryl- and heteroarylamines employs a small-ring organophosphorus-based catalyst and a terminal hydrosilane reductant to drive reductive intermolecular coupling of nitroarenes with boronic acids. Applications to the construction of both Csp2-N (from arylboronic acids) and Csp3-N bonds (from alkylboronic acids) are demonstrated; the reaction is stereospecific with respect to Csp3-N bond formation.

see article for more examples

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.

A Biphilic Phosphetane Catalyzes N-N Bond-Forming Cadogan Heterocyclization via PIII/PV=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.

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.

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

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

Key Words

arylation, amination, phenylsilane, reduction of nitro compounds

ID: J48-Y2018