Silylation reactions on nanoporous gold via homolytic Si–H activation of silanes

Si–H bond activation is an important process implicated in many useful synthetic applications including silylation and transfer hydrogenation reactions. Herein we discovered homolytic activation of Si–H bonds on the surface of nanoporous gold (NPG), forming hydrogen radicals and [Au]–[Si] intermediates. By virtue of this new reactivity, we achieved highly selective mono and sequential alcoholysis of dihydrosilane. In addition, the amphiphilic nature of the [Au]–[Si] intermediate allows for a new bis-silylation reaction of cyclic ethers. The present work showcased that the surface reactivity of nanocatalysts may provide exciting opportunity for new reaction discovery.