Synthesis
DOI: 10.1055/a-2427-9313
paper
Boryl Radical Chemistry

Amine-Ligated Boryl Radical Enabled Hydrofunctionalization of Styrenes via Halogen-Atom Transfer of Alkyl and Aryl Bromides

,
Seiya Naito
,
Koki Obata
,
This study was partially supported by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant Number JP24K17678 to N.Y.).


Abstract

Herein, we demonstrate an amine-ligated boryl radical mediated halogen-atom transfer (XAT) strategy with alkyl and aryl bromides to construct C(sp 3)–C(sp 3) and C(sp 3)–C(sp 2) bonds, respectively. The first step involves the photocatalytic and decarboxylative generation of amine-ligated boryl radicals from a carboxylic acid containing amine-ligated borane. The resulting amine-ligated boryl radical undergoes XAT with organobromides to generate carbon-centered radicals, which react with styrenes to afford hydrofunctionalized products. Furthermore, this photocatalytic XAT strategy can be applied to synthesize gem-difluorostyrene and 1,1-disubstituted cyclopropane through a radical-polar crossover mechanism.

Supporting Information



Publication History

Received: 19 August 2024

Accepted after revision: 01 October 2024

Accepted Manuscript online:
01 October 2024

Article published online:
21 October 2024

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