Palladium-catalyzed C–Si bond formation via denitrative cross-coupling of nitroarenes with hexamethyldisilane

Abstract

The transition-metal-catalyzed cross-coupling of aryl halides with silylation reagents is a powerful strategy for C(sp²)–Si bond formation. However, the need for the tedious preparation of aryl halides makes the reaction unattractive. Herein, we disclose a novel protocol for arylsilane via a Pd-catalyzed cross-coupling of hexamethyldisilane with nitroarenes, which are one of the most readily accessible chemical feedstocks. Various silylated arenes were synthesized in moderate to good yields through cleavage of the C–NO₂ bond of nitroarenes and the Si–Si bond of disilanes. These silylation products could be easily transformed into aryl halides, homocoupling products, and aryl boron reagents. Moreover, the sequential transformations of the C–Br and C–NO₂ bonds under the catalytic system exemplify the selectivity of this protocol in the late-stage modification of functional molecules.