Unparalleled Rates for the Activation of Aryl Chlorides and Bromides: Coupling with Amines and Boronic Acids in Minutes at Room Temperature

Exceptionally fast oxidative addition of an aryl chloride (or a deactivated aryl bromide) to the active Pd 0 center, which is ligated by sterically demanding phosphanes, occurs during coupling reactions catalyzed by air‐stable Pd I dimers as shown in the scheme. As a result, the reactions of aryl chlorides and bromides with amines and boronic acids at room temperature are complete within a few minutes. 1‐Ad=1‐adamantyl.