Photoredox-Catalyzed Regioselective 1,3-Alkoxypyridylation of <i>gem</i>-Difluorocyclopropanes

Difluoromethylene and pyridine cores are very important structural units in medicinal chemistry. Herein, we report the development of photoredox-catalyzed ring-opening and 1,3-alkoxypyridylation of <i>gem</i>-difluorinated cyclopropanes using 4-cyanopyrines and alcohols, employing cyclopropane radical cations as the key intermediate. The reaction exhibits high regioselectivity under mild conditions and can also be practiced on gram-scale synthesis, telescoped reaction, and late-stage functionalization of biological molecules.