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CuMgAl hydrotalcite as an efficient bifunctional catalyst for the cross-dehydrogenative C–C coupling reactions under mild conditions
Applied Catalysis A: General ( IF 5.5 ) Pub Date : 2020-08-14 , DOI: 10.1016/j.apcata.2020.117771
Weiyou Zhou , Wangmingzhu Lu , Hui Wang , Zhenzhen Xia , Shaoyan Zhai , Zhong Zhang , Yuanjun Ma , Mingyang He , Qun Chen

CuMgAl layered double hydroxide compounds (CuMgAl-LDHs) have been synthesized, characterized and investigated in the aerobic CDC reactions. The results indicated that NH3·H2O coprecipitated CuMgAl LDH (N-CuMgAl-LDH) was able to efficiently accelerate the CDC reactions between the α-Csp3–H of N-aryltetrahydroisoquinolines and nucleophiles. A wide scope of N-aryltetrahydroisoquinoline analogues and nucleophiles with different CH bonds (Csp3–H, Csp2–H and Csp–H) could be tolerated by the N-CuMgAl-LDH system. Compared with the sample using Na2CO3 as the precipitant (C-CuMgAl-LDH), N-CuMgAl-LDH showed higher catalytic activity, which probably was due to its higher surface acidity. Dual function of redox and acidity for the N-CuMgAl-LDH catalyst has been observed in the CDC reaction. According to the obtained catalytic results, kinetic isotope effect experiment and XPS analysis, iminium ion was proposed as the key intermediate, made possible by the cycle of Cu2+ and Cu+ under the aerobic conditions.



中文翻译:

CuMgAl水滑石在温和条件下可作为一种有效的双功能催化剂,用于交叉脱氢的CC偶联反应

合成了CuMgAl层状双氢氧化物(CuMgAl-LDHs),并在好氧CDC反应中进行了表征和研究。结果表明,NH 3 ·H 2 O共沉淀的CuMgAl LDH(N-CuMgAl-LDH)能够有效地促进N-四氢异喹啉的α- C sp3- H与亲核试剂之间的CDC反应。N-CuMgAl-LDH系统可以耐受具有不同C H键(C sp3- H,C sp2- H和C sp -H)的N-四氢异喹啉类似物和亲核试剂。与使用Na 2 CO 3的样品相比作为沉淀剂(C-CuMgAl-LDH),N-CuMgAl-LDH显示出较高的催化活性,这可能是由于其较高的表面酸性。在CDC反应中已观察到N-CuMgAl-LDH催化剂具有氧化还原和酸度双重功能。根据获得的催化结果,动力学同位素效应实验和XPS分析,提出了亚胺离子作为关键中间体,这是由于好氧条件下Cu 2+和Cu +的循环所致。

更新日期:2020-08-22
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