Aromatic iodonium/sulfonium rearrangement using difluoroenol silyl ethers

Difluoroenol silyl ethers are a unique class of enol silyl ethers that are widely used as a powerful difluoroalkylating reagent to incorporate difluoromethylene groups into organic molecules. In this context, we revealed a fluorine effect that the difluoroenol silyl ethers exhibit the oxygen nucleophilicity in lieu of traditional α-carbon nucleophilicity toward the aromatic iodonium/sulfonium species, thus allowing us to develop difluoroalkylative [3,3]-rearrangement of aryl iodanes and aryl sulfoxides and the difluoroalkylative dearomatization of aryl sulfoxides. In this article, we summarize these works and illustrate the logic of our design.