Synthesis of Difluorinated Heterocyclics through Metal-Free [8+1] and [4+1] Cycloaddition of Difluorocarbene

With Ph 3 P + CF 2 COO – or TMSCF 2 Br as the difluorocarbene sources, a facile metal-free cycloaddition between heteroconjugated alkenes and difluorocarbene was developed for the highly convergent synthesis of novel difluorinated heterocyclics, including gem -difluorinated azetidines and 2,3-dihydrobenzofurans. The cycloaddition features high reactivity and regioselectivity, as well as good tolerance of various electron-donating or electron-withdrawing substituents on azaheptafulvenes and o -quinone methides.