Allylic rearrangement

Organic chemistry

Combinatorial chemistry

Borylation

Electrophile

Enantioselective synthesis

Catalysis

Nucleophile

Halide

Chemistry

Alkyl

Aryl

SN2 reaction

Organocatalysis

Photochemistry

ACS Catalysis

Reported herein is a photochemical strategy for the borylation of alkyl halides using bis(catecholato)diboron as the boron source. This method exploits the ability of a nucleophilic dithiocarbonyl anion organocatalyst to generate radicals via an SN2-based photochemical catalytic mechanism, which is not reliant on the redox properties of the substrates. Therefore, it grants access to alkyl boronic esters from readily available but difficult-to-reduce electrophiles, including benzylic and allylic chlorides, bromides, and mesylates, which were inert to or unsuitable for previously reported metal-free borylation protocols.

Photochemical Organocatalytic Borylation of Alkyl Chlorides, Bromides, and Sulfonates