Phenyliodonium bis(perfltloroalkanesulfony1) methides PhI'--C(S02"2F)2 (3) were prepared by the reaction of bis(perfluoroa1kanesulfonyl)methanes with diacetoxyiodobenzene. The photochemical reactions of 3 with alkenes, methanol, bromine, and benzene gave the corresponding addition or insertion products. When 3 wm irradiated in the presence of methyl sulfide, pyridine, and triphenylphosphine, it afforded the ylides containing the bis(perfluoro-a1kanesulfonyl)mei'hylene functionality,
Y+-
-C(S02RF)2. In these reactions the bis(perf2Lloro-a1kanesulfonyl)carbene intermediate (R,SOJ2C: may be involved. Irradiation or heating of 3 in DMSO gave a 1 : I complex, the structure of which was confimed by X-ray diffraction analysis. Bis(perfluoroa1kane-sulfony1)-methylene dimethyloxosulfonium ylides Me2(0)S' --C(SO,RF), were obtained by air oxidation of bis(pevf2uoroalkanesulfonyl)methylene dimethylsulfonium ylides.
This reaction was conveniently carried out in dichloromethane at room temperature. For the preparation of 3c, a somewhat higher reaction temperature was favored (Table Two similar compounds, PhI+--C(RC0)2 and PhI+--C(PhS02)2, were prepared by the reaction of (RC02)2CH2 or (PhS02)2CH2 with PhI(OAc), under basic conditions [5-71: KOH CH2Y2 + PhI (OAc), + MeOH +-+ PhI -CY2 Y: RCO (4a) PhS02 (4b) (4)