Nickel-Photocatalytic (Z)-Selective Synthesis of Enamides from Amino Acids

(Z)-Enamides are important motifs, due to their prevalence in bio-active molecules. However, few strategies are known to obtain them stereoselectively. Herein we report a nickel catalyst which, combined with simultaneous photoredox and energy transfer catalysis, enables the selective formation of (Z)-enamides. Di- and tri- functionalized functionalized olefin products can be obtained in high yields and stereoselectivity, respectively, from a redox-modulated nickel intermediate. Selective and challenging nickel-catalyzed β-H abstraction is attainable through kinetic control facilitated by an external additive.