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

Authors：Li, Hengyuan; Zhu, Chuanle^*

Source：Journal of Organic Chemistry, 2023, 88(7): 4134-4144.

DOI：10.1021/acs.joc.2c02568

• F BOND ACTIVATION
• ALPHA
• CONSTRUCTION
• FUNCTIONALIZATION
• COPOLYMERIZATION
• ALKYLATION
• QUATERNARY
• ACCESS
• ACIDS

Purification-controlled defluorinative esterification and 1,3-dietherification of (trifluoromethyl)alkenes with alcohols are achieved, delivering various useful alpha-arylacrylates and 1,3-diethers in high yields. Remarkably, this reaction enables the cleavage of three C-F bonds in a CF3 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 alpha-arylacrylates with H2O as the oxygen source.