d <sup>0</sup> Metal-Catalyzed Alkyl–Alkyl Cross-Coupling Enabled by a Redox-Active Ligand
Roman G. Belli, Victoria C. Tafuri, Matthew V. Joannou, Courtney C. Roberts
Abstract
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.
Topics & Concepts
AlkylElectrophileChemistryLigand (biochemistry)CatalysisBeta-Hydride eliminationCoupling reactionPhotochemistryRedoxMetalCombinatorial chemistryOrganic chemistryBiochemistryReceptorCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization MethodsRadical Photochemical Reactions