Difluoromethylene-skipped enones have been readily obtained from arylvinyltriflates and aryldifluoroenoxysilanes. While these useful compounds are difficult to synthesize by the classical aldol/dehydration approach, the use of a squaramide/Li catalyst allows their direct formation via a vinyl carbocation paired with a weakly coordinating perfluorinated alkoxyaluminate. This strategy makes possible a reaction between a typically weak electrophile and a weak nucleophile. Control experiments and DFT computations shed light on the mechanism of this transformation.
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