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

An organophosphorus-catalyzed C–N bond-forming reductive coupling of nitroalkanes with arylboronic acids and esters is reported. The method shows excellent chemoselectivity for the nitro/boronic acid substrate pair, allowing the synthesis of N-(hetero)­arylamines rich in functionalization. The ident...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2022-05, Vol.144 (18), p.8242-8248
Main Authors: Li, Gen, Kanda, Yuzuru, Hong, Seung Youn, Radosevich, Alexander T.
Format: Article
Language:English
Subjects:
Alkanes
Amines
Boronic Acids
Catalysis
Nitro Compounds
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Summary:An organophosphorus-catalyzed C–N bond-forming reductive coupling of nitroalkanes with arylboronic acids and esters is reported. The method shows excellent chemoselectivity for the nitro/boronic acid substrate pair, allowing the synthesis of N-(hetero)­arylamines rich in functionalization. The identification of a sterically reduced phosphetane catalyst capable of productive coupling in the P­(III)/P­(V)O redox manifold is the key enabling development. Combined experimental kinetics and computational mechanistic studies show that the sterically reduced catalyst affects post-rate-limiting steps to enable the C–N coupling event in preference to deleterious side-paths.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.2c01487