School of Chemistry and Chemical Engineering, Key Laboratory of Functional Molecular Engineering of Guangdong Province, South China University of Technology, Guangzhou 510640, P. R. China.
J Org Chem. 2023 Apr 7;88(7):4134-4144. doi: 10.1021/acs.joc.2c02568. Epub 2023 Mar 13.
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.
实现了（三氟甲基）烯烃与醇的纯化控制脱氟酯化和 1,3-二醚化反应，以高产率得到了各种有用的α-芳基丙烯酸酯和 1,3-二醚。值得注意的是，该反应能够裂解 CF 基团中的三个 C-F 键，且无需过渡金属和催化剂，操作简单，条件温和，可规模化，具有广泛的底物范围和良好的官能团耐受性。机理研究表明，分离得到的单氟烯烃修饰的 1,3-二醚是反应的中间体，硅胶的酸性有助于这些 1,3-二醚的脱氟转化，以 HO 作为氧源得到α-芳基丙烯酸酯。
