Catalytic Enantioselective Cross-Nucleophile Coupling via Valence Tautomerism.

ABSTRACT: Valence tautomerism, traditionally underexplored in asymmetric catalysis compared to the more familiar two-electron prototropic tautomerism like keto-enol, presents a promising avenue for novel chemical transformations. In this study, we harness one-electron valence tautomerism through a dual photoredox/nickel-catalyzed system to facilitate oxidant-free, enantioselective cross-nucleophile coupling (CNC). This method efficiently couples a diverse range of β-keto esters and amides with silyl enol ethers and allyl silanes, producing coupling products that feature a quaternary stereocenter with high stereocontrol. The reaction demonstrates broad tolerance for different functional groups and molecular architectures. Mechanistic investigations, including Stern-Volmer quenching, cyclic voltammetr

SUBMITTER: Zhang Z 

PROVIDER: S-EPMC12752477 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature