Direct Access to α‐Aminosilanes Enabled by Visible‐Light‐Mediated Multicomponent Radical Cross‐Coupling

α‐Aminosilanes are an important class of organic compounds that show biological activity. In this communication, a new approach to α‐aminosilanes that utilizes photoredox catalysis to enable three‐component coupling of organo(tristrimethylsilyl)silanes with feedstock alkylamines and aldehydes is presented. A wide range of highly functionalized α‐aminosilanes can be obtained in good yields under mild conditions. Both primary amines and secondary amines are compatible with this transformation. Moreover, optically pure α‐aminosilanes are accessible by using chiral amines. Mechanistic studies indicate that reactions proceed through radical/radical cross‐coupling of silyl radicals with α‐amino alkyl radicals.