Photo-induced trifunctionalization of bromostyrenes via remote radical migration reactions of tetracoordinate boron species

Tetracoordinate boron species have emerged as radical precursors via deboronation by photo-induced single electron transfer (SET) pathway. These reactions usually produce an alkyl radical and boron-bound species, and the valuable boron species are always discarded as a by-product. Given the importance of boron species, it will be very attractive if the two parts could be incorporated into the eventual products. Herein we report a photo-catalyzed strategy in which in situ generated tetracoordinated boron species decomposed into both alkyl radicals and boron species under visible light irradiation, due to the pre-installation of a vinyl group on the aromatic ring, the newly generated alkyl radical attacks the vinyl group while leaving the boron species on ipso-position, then both radical part and boron moiety are safely incorporated into the final product. Tertiary borons, secondary borons, gem-diborons as well as 1,2-diborons, and versatile electrophiles are all well tolerated under this transformation, of note, ortho-, meta- and para-bromostyrenes all demonstrated good capabilities. The reaction portraits high atom economy, broad substrate scope, and diversified valuable products with tertiary or quaternary carbon center generated, with diborons as substrates, Csp(2)-B and Csp(3)-B are established simultaneously, which are precious synthetic building blocks in chemical synthesis. Tetracoordinate boron species are common radical precursors in organic synthesis, but the boron species are discarded as by-products. Herein the authors report a strategy to incorporate both the alkyl moiety and boron species into the eventual products, yielding organoboron compounds.

Automated summary

A photo-catalyzed strategy is reported for the incorporation of both alkyl radicals and boron species into the final products through the decomposition of tetracoordinate boron species under visible light irradiation.