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

The transition-metal-catalyzed cross-coupling of aryl halides with silylation reagents is a powerful strategy for C(sp(2))-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.

Automated summary

This study developed a novel method for the synthesis of arylsilane via Pd-catalyzed cross-coupling of hexamethyldisilane with nitroarenes. The method exhibits high selectivity and utilizes readily accessible chemical feedstocks.