One of the most widely utilized methods for the construction of C(sp²)–N bonds is the transition-metal-catalyzed cross-coupling of aryl halides/boronic acids with amines, known as Ullmann condensation, Buchwald–Hartwig amination, and Chan–Lam coupling. However, aryl halides/boronic acids often require multi-step preparation while generating a large amount of corrosive and toxic waste, making the reaction less attractive. Herein, we present an unprecedented method for the C(sp²)–N formation via Buchwald–Hartwig-type reactions using synthetically upstream nitroarenes as the sole starting materials, thus eliminating the need for arylhalides and pre-formed arylamines. A diverse range of symmetrical di- and triarylamines were obtained in a single step from nitroarenes, and more importantly, various unsymmetrical di- and triarylamines were also highly selectively synthesized in a one-pot/two-step process. Furthermore, the success of the scale-up experiments, the late-stage functionalization of a drug intermediate, and the rapid preparation of hole-transporting material TCTA showcased the utility and practicality of this protocol in synthetic chemistry. Mechanistic studies indicate that this transformation may proceed via an arylamine intermediate generated in situ from the reduction of nitroarenes, which is followed by a denitrative Buchwald–Hartwig-type reaction with another nitroarene to form a C–N bond.

We disclose a novel protocol for arylsilane via a Pd-catalyzed cross-coupling of hexamethyldisilane with nitroarenes, and the products could be easily transformed into aryl halides, homocoupling products, and aryl boron reagents.