Liu Hong-Chao, Xu Xin-Yu, Tang Siyuan, Bao Jiawei, Wang Yu-Zhao, Chen Yiliang, Han Xinya, Liang Yong-Min, Zhang Kui
School of Chemistry and Chemical Engineering, Anhui University of Technology Ma'anshan Anhui 243002 P. R. China
School of Pharmaceutical Sciences & Institute of Materia Medica, Shandong First Medical University & Shandong Academy of Medical Sciences Jinan 250117 Shandong China.
Chem Sci. 2024 Aug 6;15(36):14865-71. doi: 10.1039/d4sc03355h.
Transition-metal-catalyzed hydroarylation of unactivated alkenes metal hydride hydrogen atom transfer (MHAT) is an attractive approach for the construction of C(sp)-C(sp) bonds. However, this kind of reaction focuses mainly on using reductive hydrosilane as a hydrogen donor. Here, a novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides using protons as a hydrogen source has been developed. This reaction represents the first example of photoinduced MHAT a reductive route intercepting an organometallic coreactant. The key to this transformation was that the Co-H species was generated from the protonation of the Co intermediate, and the formed Co-C(sp) intermediate interacted with the organometallic coreactant rather than reacting with nucleophiles, a method which has been well developed in photoinduced Co-catalyzed MHAT reactions. This reaction is characterized by its high catalytic efficiency, construction of quaternary carbons, simple reaction conditions and expansion of the reactive mode of Co-catalyzed MHAT reactions a reductive route. Moreover, this catalytic system could also be applied to complex substrates derived from glycosides.
过渡金属催化的未活化烯烃的氢芳基化反应——金属氢化物氢原子转移（MHAT）是构建C(sp³)-C(sp²)键的一种有吸引力的方法。然而，这类反应主要集中于使用还原性硅烷作为氢供体。在此，已开发出一种新型的光诱导钴/镍共催化的以质子作为氢源、未活化烯烃与芳基溴化物的马氏氢芳基化反应。该反应代表了光诱导MHAT的首个实例——一条拦截有机金属共反应物的还原途径。这种转化的关键在于Co-H物种是由Co中间体的质子化产生的，并且所形成的Co-C(sp²)中间体与有机金属共反应物相互作用而非与亲核试剂反应，这是一种在光诱导钴催化的MHAT反应中已得到充分发展的方法。该反应的特点是催化效率高、构建季碳、反应条件简单以及扩展了钴催化的MHAT反应的反应模式——一条还原途径。此外，这种催化体系还可应用于糖苷衍生的复杂底物。
