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 of 1,3-dienes, activated alkyl halides, and amines is 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 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.