Synthesis and reactions of phenyliodonium bis(perfluoroalkanesulfonyl) methides

Phenyliodonium bis(perfluoroalkanesulfonyl) methides PhI +  − C(SO 2 R F ) 2 ( 3 ) were prepared by the reaction of bis(perfluoroalkanesulfonyl)methanes with diacetoxyiodobenzene. The photochemical reactions of 3 with alkenes, methanol, bromine, and benzene gave the corresponding addition or insertion products. When 3 was irradiated in the presence of methyl sulfide, pyridine, and triphenylphosphine, it afforded the ylides containing the bis(perfluoroalkanesulfonyl)methylene functionality, Y +  − C(SO 2 R F ) 2 . In these reactions the bis(perfluoroalkanesulfonyl)carbene intermediate (R F SO 2 ) 2 C: may be involved. Irradiation or heating of 3 in DMSO gave a 1 : 1 complex, the structure of which was confirmed by X‐ray diffraction analysis. Bis(perfluoroalkanesulfonyl)‐methylene dimethyloxosulfonium ylides Me 2 (O)S +  − C(SO 2 R F ) 2 were obtained by air oxidation of bis(perfluoroalkanesulfonyl)methylene dimethylsulfonium ylides.