An unprecedented catalyst-free reaction of benzo[]thiophene-2,3-diones with difluoroenoxysilanes has been developed using either MeOH or HO as the solvent, which constitutes a facile and efficient protocol for the solvent-controlled divergent synthesis of five- and seven-membered -heterocycles featuring a -difluoromethylene group. A gram-scale synthesis and the diversification of the product transformations to other difluorinated -heterocycles further highlight its utility.
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