Rongalite‐Induced Cascade CC/CO Bond Formation from Indoles, Difluoromethyl Bromides, and H2O via a Triple Cleavage Process

Herein, an efficient rongalite‐induced cascade CC/CO bond formation reaction involving indoles, difluoromethyl bromides, and H 2 O for the synthesis of indole‐3‐glyoxylates and indole‐3‐yl‐glyoxylamides has been developed. Mechanistic studies suggest that rongalite may act as a precursor of a super electron donor to activate difluoromethyl bromides for CC bond formation, as well as a source of protons to facilitate the cleavage of the CF bond for CO bond formation. The cascade reaction exhibits remarkable efficiency, broad substrate compatibility, and scalability. Moreover, the products can be further transformed into valuable heterocyclic structures and pharmacologically active compounds.