Merging Redox and Nonredox Catalysis by a Dinuclear Nickel Catalyst: Enantioselective Hydroalkoxylation of Enamides with Alcohols

The integration of fundamental redox and Lewis acid manifolds in catalysis is a pivotal goal in synthetic chemistry, promising to unlock unconventional reactivity. It typically requires two distinct metals as a single metal usually performs only one role. Therefore, achieving both functions from a single metal precursor represents an attractive, yet challenging, goal. Herein, we address this challenge through the rational design of a multifunctional ligand that features complementary coordination units for differentiating two identical metals to perform distinct functions. This ligand enables the assembly of a dinuclear Ni catalyst, wherein one Ni center acts as a Lewis acid, while the second one operates as a redox-active site. This cooperative system achieves an enantioselective hydroalkoxylation of enamides with alcohols, delivering a broad range of valuable acyclic N, O -acetals in high yields and enantioselectivities (up to 98% ee). This work opens a new avenue for the design of advanced catalytic systems.