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

Adv Synth Catal. 2020 Aug 4;362(15):3170-3182. doi: 10.1002/adsc.202000425. Epub 2020 Jun 29.

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 gem-dichloride and gem-dibromide compounds with potential for further derivatization were synthesized from simple alkenes and organohalides, like chloroform or bromoform, using low catalyst loading.

Keywords: C−C coupling; Frustrated Lewis pairs; Hydroalkylation; Molybdenum-oxido complexes; Silanes.