Copper(I)-Catalyzed Synthesis of 1-Amino-1,3-diene Derivatives through a Formal 1,3-Amino Migration Process

We present a highly efficient method utilizing a CuBr/DTBP (di-<i>tert</i>-butyl peroxide) catalyst system for the synthesis of 1-amino-1,3-diene derivatives from propargylamines and activated methylene compounds. This transformation efficiently assembles a wide range of substrates with good functional group tolerance and high atomic efficiency. Mechanistic investigations reveal that this reaction proceeds through a copper-catalyzed C-C bond formation followed by a formal 1,3-amino group migration. Notably, the C-N bond activation facilitated by cross-dehydrogenative coupling is identified as a crucial step that ensures the smooth progression of the reaction.