Catalytic Photoinduced Charge‐Transfer Osmylation: A Novel Pathway from Arenes to Cyclitol Derivatives

A catalytic, highly stereoselective one-pot synthesis of inositol and conduritol derivatives (2 and 3, respectively) from benzene (1) and other simple arenes has been achieved by excitation of the charge-transfer band of the complex between the arene and osmium tetraoxide in the presence of chlorate or bromate anions as oxygen transfer reagents. DMAP = 4-dimethylaminopyridine.