Diazoborane-Promoted Boron Insertion into Olefinic C-H Bonds.

Authors

Chonghe Zhang, Christopher C Cummins, Robert J Gilliard

Published in

Journal of the American Chemical Society. Jul 22, 2026. Epub Jul 22, 2026.

Abstract

The discovery of new borylation strategies remains a major focus in synthetic chemistry, as organoboron compounds serve as highly versatile intermediates that enable a wide range of transformations, while also playing increasingly important roles in small-molecule activation and advanced functional materials. Herein, we report a novel borylation reaction mediated by diazoboranes (RLBN₂). In contrast to conventional borylation processes, which proceed through addition to unsaturated bonds or substitution of leaving groups, diazoboranes, behaving as dicoordinate borylenes, undergo net insertion into olefinic C-H bonds. This diazoborane-mediated borylation displays a broad substrate scope, encompassing monosubstituted and gem-disubstituted olefins, as well as electron-poor and conjugated systems. Most substrates afford the E isomer with excellent selectivity (>99%). In contrast, less sterically hindered olefins exhibit partial formation of the Z isomer. Notably, acrylonitrile delivers the Z-configured product with >99% selectivity. Detailed mechanistic studies reveal that this stereochemical outcome arises from a subtle interplay between orbital interactions and steric effects during the conversion of a cyclic intermediate to the C-H activation product.

PMID:
42485502
Bibliographic data and abstract were imported from PubMed on 23 Jul 2026.

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