m-Chloroperoxybenzoic Acid Oxidation of S-Phenyl 2,2-Dimethylpropanethiosulfinate

Article abstract of DOI:10.1021/jo00139a004

At -30 deg C under nitrogen in CDCl3 the m-chloroperoxybenzoic acid (MCPBA) oxidation of S-phenyl 2,2-dimethylpropanethiosulfinate (18) leads to S-(2,2-dimethylpropyl) 2,2-dimethylpropanethiosulfonate (9), 18, S-phenyl 2,2-dimethylpropanethiosulfonate (19), 2,2-dimethylpropanesulfinic acid (20), and 2,2-dimethylpropanesulfonic acid (21).These products are consistent with attack by MCPBA at the sulfenyl sulfur atom of 18 to give α-disulfoxides 28 and at the sulfinyl sulfur atom of 18 to give 19.At 24 deg C, 18 reacts with 20 to give 19 and 2,2-dimethylpropanesulfenicacid (33), which dimerizes to S-(2,2-dimethylpropyl) 2,2-dimethylpropanethiosulfinate (5).Possible concerted, ionic, and radical mechanisms for these observations are discussed.