Cu-Catalyzed Three-Component Carbofunctionalization of 1,3-Dienes

The carboamination of 1,3-dienes provides direct and efficient access to allylic amines in a step-economical fashion. Herein, we disclose a three-component 1,3-diene carboamination reaction that provides modular access to a multitude of allylic amines. A representative scope 1,3-dienes, activated alkyl halides, and amines are demonstrated to serve as components for this reaction with yields ranging from up to 96%. High regioisomeric ratios are observed with both substituted and unsubstituted diene derivatives for either 1,2- or 1,4-carboamination (≥12:1). Mechanistic investigations demonstrate that the reaction proceeds via atom transfer radical addition (ATRA) to the diene, affording an isolable allylic halide intermediate. The scope was expanded to a general carbofunctionalization, by adding an exogenous O, S, P, or C nucleophile and base, to the reaction upon formation of the allylic halide, in a two-step, one-pot process.