Access to -Difluoromethyl Amides, (Thio)Carbamates, Ureas, and Formamides.

The first efficient access to -difluoromethyl amides, carbamates, thiocarbamates, ureas, formamides, and their derivatives is reported herein. The synthetic strategy relies on the initial synthesis and straightforward derivatization of -CFH carbamoyl fluorides, which were prepared through a desulfurization-fluorination of thioformamides (─NH─C(H)═S) coupled with carbonylation. The newly made -CFH carbonyl compounds proved to be highly robust and compatible with numerous chemical transformations and downstream derivatizations, underscoring the potential of this novel motif as a building block in complex functional molecules.