Alkylboronic acids as alkylating agents: photoredox-catalyzed alkylation reactions assisted by K(3)PO(4)

Despite the ubiquity of alkylboronic acids in organic synthesis, their utility as alkyl radical precursors in visible-light-induced photocatalytic reactions is limited by their high oxidation potentials. In this study, we demonstrated that an inorganophosphorus compound can modulate the oxidation potentials of alkylboronic acids so that they can act as alkyl radical precursors. We propose a mechanism based on the results of fluorescence quenching experiments, electrochemical experiments, (11)B and (31)P NMR spectroscopy, and other techniques. In addition, we describe a simple and reliable alkylation method that has good functional group tolerance and can be used for direct C–B chlorination, cyanation, vinylation, alkynylation, and allylation, as well as late-stage functionalization of derivatized drug molecules. Notably, alkylboronic acids can be selectively activated in the presence of a boronic pinacol ester.