d⁰ Metal-Catalyzed Alkyl–Alkyl Cross-Coupling Enabled by a Redox-Active Ligand

Alkyl–alkyl cross-coupling through well-defined mechanisms that allow for controlled oxidative addition, prevent β-hydride elimination, and tolerate hindered electrophiles is still challenging. Described herein is a redox-active ligand-enabled alkyl–alkyl cross-coupling using a d0 metal. This tris­(amido) ScIII complex as well as the oxidized variant have been thoroughly characterized (NMR, X-ray, EPR, CV, UV–vis, DFT). Insight into the likely radical nature of the mechanism is disclosed. Additionally, a substrate scope that includes functional groups incompatible with late-transition-metal catalysis and both coupling partners bearing β-hydrogens is reported.