α‑Amino Radical-Mediated Diverse Difunctionalization of Alkenes: Construction of C–C, C–N, and C–S Bonds

A general catalytic methodology for 1,2-RF/Y-difunctionalization of conjugated alkenes is reported. Diverse functionalized carbon radicals (RF•), which are generated through copper­(I)-initiated selective halogen atom abstraction via a tert-butyl hydroperoxide-induced α-amino radical process, undergo regiocontrolled addition to carbon–carbon double bonds. The newly formed carbon radicals combine with Y = CN, N3, or NCS from TMSY in a copper­(I)-promoted process to form a broad spectrum of α-cyano-, α-azido-, and α-thiocyano-β-substituted products with additional functionalities in RF in high yields. Conversion of the reaction products to functionalized cyclopropane, amide, amine, triazole, thiol, and tetrazole highlights the potential utility of this method.