Merging Photoredox and Nickel Catalysis: A Ligand-Free Cross-Coupling of Vinyl Halides and α-Silylamines toward Tertiary Allylic Alkylamines

A ligand-free cross-coupling of vinyl halides and α-silylamines toward tertiary allylic alkylamines by merging nickel and photoredox catalysis is developed. A variety of (E)-vinyl electrophiles including conjugate divinyl halides and sterically hindered vinyl halides are coupled smoothly with α-silylamines to afford allylic amines under mild conditions with good yields and E-selectivity. Moreover, by simply modifying the photocatalyst or prolonging the irradiation time, the reaction can afford Z-selective allylic amines as major products via photochemically driven E → Z isomerization. This radical-based coupling strategy provides an alternative and efficient pathway to construct tertiary allylic alkylamines with good and tunable Z/E selectivity.