Cooperative Vinylogous Enamine and Metal Catalysis

Abstract Since the first report of a dienamine‐catalyzed transformation in 2006, vinylogous enamine catalysis has been employed in conjunction with select transition metal (Cu, Ru, Pd, Ir) and lanthanide (Dy, Yb) catalysts to harness new reactivity. Collectively, these transformations have enabled alkylation and allylation at the α, γ, and ε‐positions of unsaturated aldehydes and ketones, γ‐oxyamination of enals, as well as dimerization and the formation of cyclic products via cascade reactions. In addition to their synthetic utility, these functionalization's have demonstrated the broad compatibility of vinylogous enamine intermediates with metal‐catalyzed processes spanning single electron transfer (SET), photoredox catalysis, and alkene activation. Reviewed herein are examples that have emerged since that first report in 2006.