Merging Electron Transfer Activation with 1,2-Metalate Migration: Deoxygenative Silylation of Amides

A direct deoxygenative silylation of amides with silylboronate reagents is developed in the presence of SmI2/Mg, affording a variety of high value-added alpha-aminosilane compounds in moderate to excellent yields with good functional group compatibility. The key to the success of this strategy lies in the merging of activation of amides induced by electron transfer with 1,2-metalate migration. The addition of Xantphos ligand can improve the reaction efficiency. The reactions are operationally simple and proceed under mild conditions, the raw materials are easily available and the products are highly valuable.