Metal-hydride hydrogen atom transfer (MHAT) functionalizes alkenes with predictable branched (Markovnikov) selectivity. The breadth of these transformations has been confined to π-radical traps; no sp3 electrophiles have been reported. Here we describe a Mn/Ni dual catalytic system that hydroalkylates unactivated olefins with unactivated alkyl halides, yielding aliphatic quaternary carbons.

A substrate-directed approach to couple alkylzinc nucleophiles, alkyl halide electrophiles, and non-conjugated alkenes under nickel catalysis is described.

We report a regioselective, nickel-catalyzed syn-1,2-carboamination of non-conjugated 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. File list (4) download file view on ChemRxiv Manuscript.pdf (544.78 KiB) download file view on ChemRxiv Supporting Info.pdf (40.39 MiB) download file view on ChemRxiv 3a.cif (379.57 KiB) download file view on ChemRxiv 4a.cif (835.

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