1,1-Carboamination of Terminal Alkenes via a Reaction of Azo-Ene Adducts with Grignard Reagents.

Facile conversion of petrochemical feedstocks into valuable amine molecules remains a long-standing challenge in organic chemistry. Here, we report a modular and practical alkene 1,1-carboamination technology that relies on sequential azo-ene reactions and attendant base-promoted N - N bond cleavage of azo-ene adducts with Grignard reagents. By employing allylic urazoles as imine surrogates, this method bypasses the conventional retrosynthetic logic of imine synthesis, thereby allowing for rapid access to diverse α-branched allylic amine derivatives.