Ludwig-Maximilians-Universität München, Department Chemie, Butenandtstraße 5-13, 81377 München, Germany.
Sorbonne University, Campus Pierre and Marie Curie, 4 Place Jussieu, 75005 Paris, France.
J Am Chem Soc. 2020 Mar 4;142(9):4341-4348. doi: 10.1021/jacs.9b12300. Epub 2020 Feb 20.
We report herein versatile, transition metal-free and additive-free (hetero)aryl-aryl coupling reactions promoted by the oxidative electrocoupling of unsymmetrical tetra(hetero)arylborates (TABs) prepared from ligand-exchange reactions on potassium trifluoroarylborates. Exploiting the power of electrochemical oxidations, this method complements the existing organoboron toolbox. We demonstrate the broad scope, scalability, and robustness of this unconventional catalyst-free transformation, leading to functionalized biaryls and ultimately furnishing drug-like small molecules, as well as late stage derivatization of natural compounds. In addition, the observed selectivity of the oxidative coupling reaction is related to the electronic structure of the TABs through quantum-chemical calculations and experimental investigations.
我们在此报告了一种多功能、无过渡金属和添加剂的（杂）芳基-芳基偶联反应，该反应由通过钾三氟芳基硼酸酯的配体交换反应制备的不对称四（杂）芳基硼酸酯（TAB）的氧化电化学偶联来促进。利用电化学氧化的强大功能，这种方法补充了现有的有机硼工具箱。我们展示了这种非传统无催化剂转化的广泛的范围、可扩展性和稳健性，得到了功能化的联芳烃，并最终提供了类似药物的小分子，以及天然化合物的后期衍生化。此外，通过量子化学计算和实验研究，观察到氧化偶联反应的选择性与 TAB 的电子结构有关。
