Litcius/Paper detail

Cooperative Bimetallic Catalysis via One‐Metal/Two‐Ligands: Mechanistic Insights of Polyfluoroarylation‐Allylation of Diazo Compounds

Gao‐Yin Wang, Zhaoliang Ge, Kuiling Ding, Xiaoming Wang

2023Angewandte Chemie International Edition20 citationsDOI

Abstract

Metal/ligand in situ assembly is crucial for tailoring the reactivity & selectivity in transition metal catalysis. Cooperative catalysis via a single metal/two ligands is still underdeveloped, since it is rather challenging to harness the distinct reactivity profiles of the species generated by self-assembly of a single metal precursor with a mixture of different ligands. Herein, we report a catalytic system composed of a single metal/two ligands for a three-component reaction of polyfluoroarene, α-diazo ester, and allylic electrophile, leading to highly efficient construction of densely functionalized quaternary carbon centers, that are otherwise hardly accessible. Mechanistic studies suggest this reaction follows a cooperative bimetallic pathway via two catalysts with distinct reactivity profiles, which are assembled in situ from a single metal precursor and two ligands and work in concert to escort the transformation.

Topics & Concepts

Bimetallic stripReactivity (psychology)CatalysisDiazoChemistryLigand (biochemistry)ElectrophileCombinatorial chemistryMetalSelectivitySynergistic catalysisHydroformylationOrganic chemistryRhodiumReceptorAlternative medicinePathologyMedicineBiochemistryCyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling Reactions