Redox Catalysis Involving Substrate Photooxidation with Catalyst Regeneration bySubstrate Reduction. Simultaneous Oxidative C-H Bond Cleavage and Reductive C-S Bond Cleavage in Thioethers Catalyzed by W10O324-

摘要

Several experiments examining the photooxidation of thioethers bypolyoxotungstates have established that it can be used to effect both substrate photooxidation and reduction in the same reaction. Under anaerobic conditions in solution at ambient temperature the excited state reacts with thioethers in high selectivity by a hydrogen abstraction to form the carbon radicals. The principal reduced form of the catalyst reduces thioethers to effect C-S bond cleavage, thus the net observed products in anaerobic photooxidation of these substrates catalyzed are the dimers resulting from coupling of the alpha-carbon radicals and C-S bond cleavage products including the hydrocarbon resulting from complete desulfurization of the thioether.