Divergent Construction of α,α-Difunctionalized Ketones via [1,2]-Sigmatropic Rearrangement/Alkylation-Hydroxylation/Dialkylation of I^(III)/S^(VI) Ylides

The rare [1,2]-sigmatropic rearrangement of sulfoxonium-iodonium hybrid ylides is described, which enables the efficient sulfoxidation/sulfonylation-alkylation of I^(III)/S^(VI) ylides with 1,3-dicarbonyls. By slight modification of the reaction conditions, controllable alkylation-hydroxylation and dialkylation of I^(III)/S^(VI) ylides were achieved. This strategy affords a diverse array of α,α-difunctionalized ketones in moderate to good yields, demonstrating broad substrate scope. These findings provide an important advancement in the [1,2]-sigmatropic rearrangement of sulfoxonium ylides and highlight the divergent reactivity of I^(III)/S^(VI) ylides.