Spatial Anion Control on Palladium for Mild C–H Arylation of Arenes

C–H arylation of arenes without
the use of directing groups
is a challenge, even for simple molecules, such as benzene. We describe
spatial anion control as a concept for the design of catalytic sites
for C–H bond activation, thereby enabling nondirected C–H
arylation of arenes at ambient temperature. The mild conditions enable
late-stage structural diversification of biologically relevant small
molecules, and site-selectivity complementary to that obtained with
other methods of arene functionalization can be achieved. These results
reveal the potential of spatial anion control in transition-metal
catalysis for the functionalization of C–H bonds under mild
conditions.

无需使用导向基团（directing groups）的芳烃C–H芳基化（C–H arylation）反应，即便对于苯这类简单分子而言，亦是一项极具挑战性的课题。我们提出空间阴离子调控（spatial anion control）作为设计C–H键活化（C–H bond activation）催化位点的新概念，由此实现了室温（ambient temperature）条件下芳烃的无导向C–H芳基化反应。该反应条件温和，可实现生物相关小分子的后期结构多样化（late-stage structural diversification）修饰，且能获得与其他芳烃功能化方法互补的位点选择性（site-selectivity）。上述研究结果揭示了空间阴离子调控在过渡金属催化（transition-metal catalysis）领域中，用于温和条件下C–H键功能化的应用潜力。