Catalytic Imine C–H Alkylation Methods and Novel Three-component Paths to Allylic Amines

The thesis describes development of C–H alkylation of imine-type compounds and three- component assembly of allylic amines. First, a general and efficient method of C–H alkylation of formaldoximes was developed. The protocol unifies light-induced hybrid palladium radical chemistry with oxidative properties of palladium. As a result, this protocol allows for coupling of primary, secondary and tertiary alkyl bromides or iodides with variety of terminal oximes under very mild conditions. Second, the logic was further translated onto glyoxylate-derived hydrazones, achieving C–H alkylation of the latter. In addition to alkyl halides, the method can also engage redox-active esters. Mildness of the method, as well as mechanistic features enabled synthesis of otherwise hard-to-access E isomers, and to approach unusual heterocycles. Next, a protocol for homologative three-component synthesis of allylic amines was developed. Merging of the light-induced alkyl-Heck reaction with the classical Tsuji-Trost chemistry enabled rapid access to allylic amines of various structures. Method also features potential for the stereoselective transformations.