The Buchwald-Hartwig Amination after 25 Years.

The Pd-catalyzed coupling of aryl (pseudo)halides and amines is one of the most powerful approaches for the formation of C(sp(2))-N bonds. The pioneering reports from Migita and subsequently Buchwald and Hartwig on the coupling of aminostannanes and aryl bromides rapidly evolved into general and practical tin-free protocols with broad substrate scope, which led to the establishment of what is now known as the Buchwald-Hartwig amination. This Minireview summarizes the evolution of this cross-coupling reaction over the course of the past 25 years and illustrates some of the most recent applications of this well-established methodology.