An enantioselective synthesis of anthrone-derived NHPI analogues has been developed. One of these analogues, in combination with Co salts, was employed to catalyse the aerobic oxidation of benzylic compounds and diols. Exploratory studies using a racemic version of the catalyst were also conducted. Radical addition of dioxolanes or alcohols to activated alkenes with molecular oxygen as the terminal oxidant was also shown to be catalysed with NHPI analogues.