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

With Ph₃P⁺CF₂COO^– or TMSCF₂Br 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.