Zhang Pengfei, Jiang Zhiwei, Fan Zhoulong, Li Guoshuai, Ma Qingxue, Huang Jun, Tang Jinghong, Xu Xiaohua, Yu Jin-Quan, Jin Zhong
College of Chemistry, State Key Laboratory of Elemento-organic Chemistry, Nankai University Tianjin 300071 China
Department of Chemistry, The Scripps Research Institute La Jolla CA 92037 United States
Chem Sci. 2023 Jul 7;14(31):8279-8287. doi: 10.1039/d3sc01670f. eCollection 2023 Aug 9.
The synthesis of macrocyclic compounds with different sizes and linkages remains a great challenge transition metal-catalysed intramolecular C-H activation. Herein, we disclose an efficient macrocyclization strategy Pd-catalysed remote -C-H olefination using a practical indolyl template. This approach was successfully employed to access macrolides and coumarins. In addition, the intermolecular -C-H olefination also worked well and was exemplified by the synthesis of antitumor drug belinostat from inexpensive and readily available benzenesulfonyl chloride. Notably, catalytic copper acetate and molecular oxygen were used in place of silver salts as oxidants. Furthermore, for the first time, the formation of a macrocyclophane cyclopalladated intermediate was detected through Fourier-transform infrared monitoring experiments and ESI-MS.
通过过渡金属催化的分子内C-H活化来合成具有不同尺寸和连接方式的大环化合物仍然是一个巨大的挑战。在此，我们披露了一种高效的大环化策略，即使用实用的吲哚基模板通过钯催化的远程C-H烯基化反应。该方法已成功用于合成大环内酯和香豆素。此外，分子间C-H烯基化反应也表现良好，以从廉价且易于获得的苯磺酰氯合成抗肿瘤药物贝利司他为例。值得注意的是，使用催化量的醋酸铜和分子氧代替银盐作为氧化剂。此外，首次通过傅里叶变换红外监测实验和电喷雾电离质谱检测到了大环环钯化中间体的形成。
