Direct arylation of arene C-H bonds by cooperative action of NHCarbene-Ruthenium(II) catalyst and carbonate via proton abstraction mechanism

Ozdemir, IsmailDemir, SerpilCetinkaya, BekirGourlaouen, ChristopheMaseras, FeliuBruneau, ChristianDixneuf, Pierre H.2024-08-042024-08-0420080002-7863https://doi.org/10.1021/ja710276xhttps://hdl.handle.net/11616/94443Direct functionalization of sp(2) C-H bonds via ortho diarylation of 2-pyridyl benzene with arylbromides was achieved using ruthenium(II) catalysts containing a RuCl2(NHC) unit and generated from [RuCl2(arene)](2) and two types of NHC precursors, pyrimidinium and benzimidazolium salts, in the presence of Cs2CO3. DFT calculations from RuCl2(NHC)(2-pyridylbenzene) show that a proton abstraction mechanism, on cooperative actions of both the coordinated base and the Ru(II) center, is favoured via a 13.7 kcal mol(-1) exothermic process affording an orthometalated intermediate with a 2.009 angstrom Ru-C bond.eninfo:eu-repo/semantics/closedAccessAryl ChloridesIntramolecular ArylationRuthenium ComplexesMultiple ArylationCoupling ReactionsPhosphine OxidesOrganic HalidesActivationDerivativesBromidesDirect arylation of arene C-H bonds by cooperative action of NHCarbene-Ruthenium(II) catalyst and carbonate via proton abstraction mechanismArticle13041156+1818398710.1021/ja710276x2-s2.0-38649141502N/AWOS:000252634600022Q1