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Presented herein is an intriguing effect of fluorine, and it allows difluoroenol silyl ethers to couple with aryliodanes in a redox‐neutral manner to afford ortho‐iodo difluoroalkylated arenes. The remaining iodide group provides a versatile platform for converting the products into various valuable difluoroalkylated arenes. The reaction shows excellent functional‐group compatibility and broad substrate scope. A DFT mechanistic study suggests that the fluorine effect facilitates a subtle nucleophilic attack of the oxygen atom of enol silyl ethers onto aryliodanes, therefore leading to a rearrangement. Taking effect: An intriguing effect of fluorine in difluoroenol silyl ether distinguishes it from other enol silyl ethers by enabling its cross‐coupling with aryliodanes. This reaction represents the first cross‐coupling of enol silyl ethers by rearrangement, and involves concomitant reduction of iodine(III) to iodine(I). Tf=trifluoromethylsilyl, TMS=trimethylsilyl. [ABSTRACT FROM AUTHOR]

Presented herein is an intriguing effect of fluorine, and it allows difluoroenol silyl ethers to couple with aryliodanes in a redox‐neutral manner to afford ortho‐iodo difluoroalkylated arenes. The remaining iodide group provides a versatile platform for converting the products into various valuable difluoroalkylated arenes. The reaction shows excellent functional‐group compatibility and broad substrate scope. A DFT mechanistic study suggests that the fluorine effect facilitates a subtle nucleophilic attack of the oxygen atom of enol silyl ethers onto aryliodanes, therefore leading to a rearrangement. [ABSTRACT FROM AUTHOR]