Novel highly regioselective VO(acac)2/TBHP mediated oxidation of o-alkenyl phenols to o-hydroxybenzyl ketones

A novel mild methodology for the preparation of o-hydroxybenzyl ketones is described starting from o-alkenyl phenols and based on the VO(acac)(2)/TBHP (2 mol %/1.2 equiv) system. VO(acac)(2) first catalyzes the epoxidation of o-alkenyl phenols and then the rearrangement of the epoxyphenols to ketones via the selective benzylic C-O cleavage and 1,2 hydride migration. The protocol has also been applied to set up a useful and easy one-pot conversion of o-alkenyl phenols to benzo[b]furans by means of the sequential addition of TFA, after the generation of the intermediate o-hydroxybenzyl ketones.