Directed, Nickel-Catalyzed Umpolung 1,2-Carboamination of Alkenyl Carbonyl Compounds

Abstract

We report a regioselective, nickel-catalyzed syn-1,2-carboamination of nonconjugated alkenyl carbonyl compounds with O-benzoyl hydroxylamine (N–O) electrophiles and aryl/alkylzinc nucleophiles to afford β- and γ-amino acid derivatives. This method enables preparation of products containing structurally diverse tertiary amine motifs, including heterocycles, and can also be used to form quaternary carbon centers. The reaction takes advantage of a tethered 8-aminoquinoline directing group to control the regiochemical outcome and suppress two-component coupling between the N–O electrophile and organozinc nucleophile.