Conversion of trifluoromethyl into ester along with polyethers upcycling by cation-transfer catalyzed C–O/C–F metathesis

Abstract

Ester and trifluoromethyl groups play crucial roles in chemistry and drug design. However, the implementation of interconvesion from trifluoromethyl into ester under wide condition is not an easy work because the C–F bond of trifluoromethyl group possesses high bond energy and extremely difficult to break. Herein, we for the first time present a silylium-ion-initiated method for intermolecular C–F/C–O metathesis, enabling selective activation of inert C(sp3)–F and C(sp3)–O bonds. This approach facilitates the defluoroalkoxylation of trifluoromethyl-substituted substrates and polyfluoroalkanes when combined with ethers or polyethers, thus builds a bridge to convert trifluoromethyl groups into ester/ketone groups along with polyethers upcycling. We provided crystallographic evidence to clearly confirm that this reaction involves the formation of silyloxonium ions and Meerwein-type salt intermediates, followed by cationic ligand transformations.