Nitrogen donor-controlled chemoselectivity of reaction in oxidation of sulfides with tetra-n-butylammonium hydrogen monopersulfate catalyzed by a partially β-brominatedmeso-tetraphenylporphyrinatomanganese(III) acetate: a clue to the nature of active oxidant

Highly efficient and rapid oxidation of different sulfides to the corresponding sulfones with tetra-n- butylammonium hydrogen monopersulfate (TBAO) in the presence of catalytic amounts of Mn(TPPBr2)OAc at room temperature is reported. Contrary to other nitrogen donors, using 4-cyanopyridine as co-catalyst leads to an increase in the ratio of sulfoxide to sulfone in the products. Comparison of the chemoselectivity of reaction in the presence of different nitrogen donors as co-catalyst shows the involvement of a high-valent Mn-oxo species as well as the six-coordinate Mn(TPPBr2)(HSO5)(B) (B = nitrogen donors) complex in sulfide oxidation reactions with TBAO.