Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, 518055, China.
Academy for Advanced Interdisciplinary Studies and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
Angew Chem Int Ed Engl. 2020 Sep 21;59(39):16926-16932. doi: 10.1002/anie.202006317. Epub 2020 Aug 20.
We describe a photoinduced copper-catalyzed asymmetric radical decarboxylative alkynylation of bench-stable N-hydroxyphthalimide(NHP)-type esters of racemic alkyl carboxylic acids with terminal alkynes, which provides a flexible platform for the construction of chiral C(sp )-C(sp) bonds. Critical to the success of this process are not only the use of the copper catalyst as a dual photo- and cross-coupling catalyst but also tuning of the NHP-type esters to inhibit the facile homodimerization of the alkyl radical and terminal alkyne, respectively. Owing to the use of stable and easily available NHP-type esters, the reaction features a broader substrate scope compared with reactions using the alkyl halide counterparts, covering (hetero)benzyl-, allyl-, and aminocarbonyl-substituted carboxylic acid derivatives, and (hetero)aryl and alkyl as well as silyl alkynes, thus providing a vital complementary approach to the previously reported method.
我们描述了一种光诱导的铜催化不对称自由基脱羧炔基化反应，该反应可将稳定的 N-羟基邻苯二甲酰亚胺（NHP）型酯与末端炔烃进行对映选择性烷基羧酸反应，为构建手性 C(sp )-C(sp)键提供了一个灵活的平台。该反应的成功关键不仅在于使用铜催化剂作为双光和交叉偶联催化剂，还在于对 NHP 型酯进行调节，以分别抑制烷基自由基和末端炔烃的易位二聚化。由于使用了稳定且易于获得的 NHP 型酯，与使用烷基卤化物反应相比，该反应具有更广泛的底物范围，包括（杂）苄基、烯丙基和氨甲酰基取代的羧酸衍生物，以及（杂）芳基和烷基以及硅基炔烃，从而为之前报道的方法提供了重要的补充方法。
