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.