Tlahuext-Aca Adrian, Lee Sarah Yunmi, Sakamoto Shu, Hartwig John F
Department of Chemistry, University of California Berkeley, Berkeley, California 94720, United States.
ACS Catal. 2021 Feb 5;11(3):1430-1434. doi: 10.1021/acscatal.0c05254. Epub 2021 Jan 14.
The direct, catalytic arylation of simple arenes in small excess with aryl bromides is disclosed. The developed method does not require the assistance of directing groups and relies on a synergistic catalytic cycle in which phosphine-ligated silver complexes cleave the aryl C-H bond, while palladium catalysts enable the formation of the biaryl products. Mechanistic experiments, including kinetic isotope effects, competition experiments, and hydrogen-deuterium exchange, support a catalytic cycle in which cleavage of the C-H bond by silver is the rate-determining step.
本文公开了一种使用少量过量的简单芳烃与芳基溴进行直接催化芳基化反应的方法。所开发的方法不需要导向基团的辅助，而是依赖于一种协同催化循环，其中膦配位的银配合物裂解芳基C-H键，而钯催化剂促进联芳基产物的形成。包括动力学同位素效应、竞争实验和氢-氘交换在内的机理实验支持了一种催化循环，其中银对C-H键的裂解是速率决定步骤。
