Nonconventional driving force for selective oxidative C-C coupling reaction due to concurrent and curious formation...

Is it possible to 'explore' metal's intrinsic property-a cohesive interaction-which naturally transform M⁰ into an aggregate or a particle or film for driving oxidative C-C bond formation? With this intention, reduction of [Ag(NH₃)₂]⁺ to Ag⁰ with concurrent oxidation of different phenols/naphthols to biphenyls was undertaken. The work is originated during careful observation of an undergraduate experiment-Tollens' test-where silver mirror film deposition takes place on the walls of borosilicate glass test tube. When the same reaction was carried out in polypropylene (plastic-Eppendorf) tube, we observed aggregation of Ag⁰ leading to floating Ag-particles but not silver film deposition. This prompted us to carry out challenging cross-coupling reaction by ONLY changing the surface of the reaction flask from glass to plastic to silicones. To our surprise, we observed good selective oxidative homo-coupling on Teflon surface while cross-coupling in Eppendorf vial. Thus, we propose that the formation of biphenyl is driven by the macroscopic growth of Ag⁰ into [Ag-particle] orchestrated by Ag…Ag cohesive interaction. To validate results, experiments were also performed on gram scale. More importantly, oxidation of β-naphthol carried out in quartz (chiral) tube which yielded slight enantioselective excess of BINOL. Details are discussed.