Defluorinative Esterification and 1,3-Dietherification of (Trifluoromethyl)alkenes with Alcohols: Controlled Synthesis of α-Arylacrylates and 1,3-Diethers.

Purification-controlled defluorinative esterification and 1,3-dietherification of (trifluoromethyl)alkenes with alcohols are achieved, delivering various useful α-arylacrylates and 1,3-diethers in high yields. Remarkably, this reaction enables the cleavage of three C-F bonds in a CF group, and it is transition-metal free and catalyst-free, has simple operation, features mild conditions, is gram-scalable, and has broad substrate scope and valuable functional group tolerance. Mechanism studies indicated that the isolated monofluoroalkene-decorated 1,3-diethers are the intermediates, and the acidic property of silica gel assisted the defluorinative transformation of these 1,3-diethers to access α-arylacrylates with HO as the oxygen source.