Synthetic applications of arylboronic acid via an aryl radical transfer pathway.

The transition-metal-catalyzed functionalization of arylboronic acids is the most powerful tool for the formation of carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. These transformations are generally considered to proceed via organometallic intermediates generated by transmetalation from the boronic acids. Interestingly, there is a novel recognition that arylboronic acids can serve as aryl radical precursors via oxidative carbon-boron bond cleavage in recent years. Manganese(III) acetate, Ag(I)/persulfate and iron(II or III)/persulfate catalytic systems have been shown to be effective for this transformation. In this review, recent advances in this new area are highlighted and their mechanisms are also discussed.