Introducing the Catalytic Amination of Silanes via Nitrene Insertion

Abstract

The direct functionalization of Si−H bonds by the nitrene insertion methodology is described. A copper(I) complex bearing a trispyrazolylborate ligand catalyzes the transfer of a nitrene group from PhINTs to the Si−H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si−NH moieties in the first example of this transformation. The process tolerates other functionalities in the substrate such as several C−H bonds and alkyne and alkene moieties directly bonded to the silicon center. Density functional theory (DFT) calculations provide a mechanistic interpretation consisting of a Si−H homolytic cleavage and subsequent rebound to the Si-centered radical.