Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, P. R. China.
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, 510640, P. R. China.
Angew Chem Int Ed Engl. 2017 Oct 16;56(43):13324-13328. doi: 10.1002/anie.201707719. Epub 2017 Sep 22.
The first oxidative C(sp )-H/C(sp )-H cross-dehydrogenative coupling (CDC) reaction promoted by an internal oxidant is reported. This copper-catalyzed CDC reaction of oxime acetates and trifluoromethyl ketones provides a simple and efficient approach towards 2-trifluoromethyldihydropyrrol-2-ol derivatives in a highly diastereoselective manner by cascade C(sp )-C(sp ) bond formation and cyclization. These products were further transformed into various significant and useful trifluoromethylated heterocyclic compounds, such as trifluoromethylated furan, thiophene, pyrrole, dihydropyridazine, and pyridazine derivatives. A trifluoromethylated analogue of an Aβ lowering agent was also synthesized smoothly. Preliminary mechanistic studies indicated that this reaction involves a copper(I)/copper(III) catalytic cycle with the oxime acetate acting as an internal oxidant.
首次报道了由内源性氧化剂促进的首例氧化 C(sp )-H/C(sp )-H 交叉脱氢偶联（CDC）反应。该铜催化肟乙酸盐和三氟甲基酮的 CDC 反应以高度非对映选择性方式通过级联 C(sp )-C(sp ) 键形成和环化，提供了一种简单有效的方法，用于合成 2-三氟甲基二氢吡咯-2-醇衍生物。这些产物可以进一步转化为各种重要且有用的三氟甲基杂环化合物，如三氟甲基呋喃、噻吩、吡咯、二氢哒嗪和哒嗪衍生物。还顺利地合成了 Aβ 降低剂的三氟甲基类似物。初步的机理研究表明，该反应涉及铜（I）/铜（III）催化循环，其中肟乙酸盐作为内源性氧化剂。
