Anodic carbon–boron bond cleavage through the intermediacy of electrogenerated bromonium ion

The electrochemical properties of a series of cyclic arylboronic esters, XC6H4B(OR)2 [RR = CH2CH2; X = H (1a); p-Me (1b); p-OMe (1c); p-Cl (1d); p-Ph (1e); m-Cl (1f); m-OMe (1g); CF3 (1h); OMe (1i); 2,6-dimethyl (1j); 1b with RR = (CH2)3, (1k); 1b with RR = CMe2CMe2, (1m)] has been studied in acetonitrile by cyclic voltammetry (CV) and controlled-potential electrolysis (CPE). The CV of representative examples of aryl borates with different substituents show one irreversible oxidation wave on a Pt cathode, at 1.8–1.9 V (vs. Ag/AgCl), with a negligible substituent effect. The cathodic CPE process led to small amounts of biaryls only, whereas the direct anodic CPE could not be carried out practically due to low currents. However, in the presence of electrogenerated bromonium (or iodonium) ions a C–B bond cleavage does take place to yield the corresponding bromoaryls, brominated phenols, and arylboronic acids as the major products.