Jiang Zhong-Tao, Huang Jiangkun, Zeng Yaxin, Hu Fangdong, Xia Ying
West China School of Public Health and West China Fourth Hospital, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu, 610041, China.
School of Chemistry and Chemical Engineering, Linyi University, Linyi, 276005, China.
Angew Chem Int Ed Engl. 2021 May 3;60(19):10626-10631. doi: 10.1002/anie.202016258. Epub 2021 Mar 30.
Herein, we report a rhodium catalyzed directing-group free regioselective C-H allylation of simple arenes. Readily available gem-difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via a sequence of C-C and C-F bond activation, providing allyl arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late-stage functionalization of complex bioactive molecules. The high efficiency of this reaction is also demonstrated by the high turnover number (TON, up to 1700) of the rhodium catalyst on gram-scale experiments. Preliminary success on kinetic resolution of this transformation is achieved, providing a promising access to enantio-enriched gem-difluorinated cyclopropanes.
在此，我们报道了一种铑催化的简单芳烃无导向基团区域选择性C-H烯丙基化反应。通过一系列C-C和C-F键活化，易于获得的偕二氟环丙烷可用作高反应活性的烯丙基替代物，在温和条件下以良好的产率和高区域选择性提供烯丙基芳烃衍生物。该稳健的方法能够实现复杂生物活性分子的便捷后期官能团化。在克级实验中，铑催化剂的高周转数（TON，高达1700）也证明了该反应的高效率。该转化的动力学拆分取得了初步成功，为对映体富集的偕二氟环丙烷提供了一条有前景的途径。
