Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs

Abstract

Three molybdenum(VI) dioxido complexes [MoO₂(L)₂] bearing Schiff base ligands were reacted with B(C₆F₅)₃ to afford the corresponding adducts [MoO{OB(C₆F₅)₃}(L)₂], which were fully characterized. They exhibit Frustrated Lewis-Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C₆F₅)₃}(L)₂] complex with L=2,4-dimethyl-6-((phenylimino)methyl)phenol proved to be active as catalyst for the hydroalkylation of aryl alkenes with organohalides and for the Atom-Transfer Radical Addition (ATRA) of organohalides to aliphatic alkenes. A series of <i>gem</i>-dichloride and <i>gem</i>-dibromide compounds with potential for further derivatization were synthesized from simple alkenes and organohalides, like chloroform or bromoform, using low catalyst loading.