Complementary Tandem\nReaction Manifolds and “Switch\nMechanisms” in the Reaction of Epoxides with Selectfluor

Tandem reactions are highly sought after transformations\nin organic\nsynthesis as they accomplish multiple steps at once and can serve\nas golden keys unlocking mechanistic complexities. Reactions that\noperate through different mechanisms depending on the conditions (“switch\nmechanisms”) are of intense interest to organic chemists as\nfonts of new reactivity. We report that Selectfluor can catalyze the\nrearrangement of 1,1-disubstituted epoxides, providing a new approach\nto benzylic fluorination. These results complement earlier work involving\nradical-cation-based ring opening of epoxides.