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

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.