Rh(III)‐Catalysed Switchable and Chemoselective Synthesis of Difluorinated Pyrazolo[1,2‐a]indazolone and Indole Frameworks

Abstract Different from the classical defluorinated process for gem‐difluoromethylene alkynes, described herein is the chemodivergent synthesis of difluorinated pyrazolo[1,2‐a]indazolone and indole frameworks via Rh(III)‐catalysed regioselective C−H functionalization of phenidone with gem‐difluoromethylene alkynes in a switchable manner. The detailed reaction pathways and the origin of chemoselectivity were clarified through a combined experimental and computational mechanistic study, which involves different quench modes of C−Rh bond via protonolysis or C−N bond reductive elimination switched by the solvent