Metal-Free Iodine/TEMPO-Mediated Aerobic Oxidative Ugi-Type Multicomponent Reactions with Tertiary Amines

A novel aerobic oxidative Ugi-type multicomponent reaction (MCR) with tertiary amines was developed. The reaction was initiated by C(sp3)–H oxidation of the amine, followed by nucleophilic attack on the highly reactive isocyanide, generating nitrilium ion intermediates. If these intermediates were trapped by water in the system, α-amido amines could be delivered as the Ugi-3CR products. If exogenous TMSN3 was added, α-tetrazolo amines could be furnished as the first example of oxidative Ugi-azide MCR products.