Rhodium(II)-catalyzed transylidation of aryliodonium ylides: Electronic effects of aryl groups determine their thermodynamic stabilities

Intermolecular transylidations between aryliodonium ylides under catalytic conditions were developed. Heating a solution of phenyliodonium bis(trifluoromethylsulfonyl)methylide in a large amount (80 equiv) of a substituted iodobenzene in the presence of 5 mol % of rhodium(II) acetate as a catalyst transfers the bis(trifluoromethylsulfonyl)-methylidene group to the iodine(I) atom and affords a substituted aryliodonium ylide in a good yield. Reversible nature of the catalytic intermolecular transylidation makes it possible to evaluate the thermodynamic stability of aryliodonium ylides.