Tunable Synthesis of Monofluoroalkenes and Gem‐Difluoroalkenes via Solvent‐Controlled Rhodium‐Catalyzed Arylation of 1‐Bromo‐2,2‐difluoroethylene

Abstract Divergent synthesis of fluorine‐containing scaffolds starting from a suite of raw materials is an intriguing topic. Herein, we report the solvent‐controlled rhodium‐catalyzed tunable arylation of 1‐bromo‐2,2‐difluoroethylene. The selection of the reaction solvents provides switchable defluorinated or debrominated arylation from readily available feedstock resources (both arylboronic acids/esters and 1‐bromo‐2,2‐difluoroethylene are commercially available). This switch is feasible because of the difference in coordination ability between the solvent (CH 2 Cl 2 or CH 3 CN) and the rhodium center, resulting in different olefin insertion. This protocol allows the convenient synthesis of monofluoroalkenes and gem‐ difluoroalkenes, both of which are important scaffolds in the fields of medicine and materials. Moreover, this newly developed solvent‐regulated reaction system can be applied to the site‐selective dechlorinated arylation of trichloroethylene. Overall, this study provides a useful strategy for the divergent synthesis of fluorine‐containing scaffolds and provides insight into the importance of solvent selection in catalytic reactions.