Dual Nickel/Photoredox-Catalyzed Site-Selective Cross-Coupling of 1,2-Bis-Boronic Esters Enabled by 1,2-Boron Shifts.

ABSTRACT: Site-selective transition-metal-catalyzed mono-deboronative cross-couplings of 1,2-bis-boronic esters are valuable methods for the synthesis of functionalized organoboron compounds. However, such cross-couplings are limited to reaction of the sterically less hindered primary boronic ester. Herein, we report a nickel/photoredox-catalyzed mono-deboronative arylation of 1,2-bis-boronic esters that is selective for coupling of the more sterically hindered secondary/tertiary position. This is achieved by taking advantage of a 1,2-boron shift of primary β-boryl radicals to the thermodynamically favored secondary/tertiary radicals, which are subsequently intercepted by the nickel catalyst to enable arylation. The mild conditions are amenable to a broad range of aryl halides to give β-aryl boronic

SUBMITTER: Wang H 

PROVIDER: S-EPMC9543306 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature