Centro de Investigaciones Científicas Avanzadas (CICA) and Departamento de Química, Universidade da Coruña, E-15071 A Coruña, Spain.
Molecules. 2018 Jun 29;23(7):1582. doi: 10.3390/molecules23071582.
The activation of C⁻H bonds through catalytic reactions using transition metals is an important challenge in organic chemistry in which the intermediates are related to those produced in the classical cross-coupling reactions. As part of our research program devoted to the development of metal-catalyzed reactions using indium organometallics, a protocol for the C⁻H activation and C⁻C coupling of 2-arylpyridines with triorganoindium reagents under Rh(I) catalysis is reported. Under the optimized conditions, we found that Me₃In and Ar₃In reagents reacted with 2-arylpyridines and related compounds in the presence of Rh(PPh₃)₃Cl, in PhCl/THF (9:1), at 120 °C for 48 h, to afford the -coupling products in moderate to good yields. The nitrogen atom in the pyridine ring acts as a directing group to assist the functionalization at the position of the aryl group forming a new C⁻C bond at this position.
通过使用过渡金属的催化反应激活 C-H 键是有机化学中的一个重要挑战，其中中间体与经典交叉偶联反应中产生的中间体有关。作为我们致力于使用铟有机金属开发金属催化反应的研究计划的一部分，报道了在 Rh(I)催化下使用三有机铟试剂对 2-芳基吡啶进行 C-H 激活和 C-C 偶联的方案。在优化条件下，我们发现 Me₃In 和 Ar₃In 试剂在 Rh(PPh₃)₃Cl 的存在下，在 PhCl/THF（9:1）中于 120°C 反应 48 小时，可中等至良好产率得到 -偶联产物。吡啶环中的氮原子作为导向基团，辅助芳基的 位官能化，在该位置形成新的 C-C 键。
