Rempala, Pawel Kroulík, Jiří King, Benjamin T. Investigation of the Mechanism of the Intramolecular Scholl Reaction of Contiguous Phenylbenzenes Two mechanisms of the Scholl reaction were investigated in the series 1, 2, ..., <i>n</i>-oligophenylbenzenes (<i>n</i> = 2, 3, 4, 6) at the B3LYP/6-31G(d) level of theory. A mechanism involving generation of a radical cation followed by C−C bond formation and dehydrogenation is unlikely on the basis of unfavorable energies of activation. A mechanism involving generation of an arenium cation followed by C−C bond formation and dehydrogenation is energetically feasible. An explanation for the facile polycondensation of hexaphenylbenzene to hexa-<i>peri</i>-hexabenzocoronene, where six new aryl−aryl bonds are formed, is provided. Kinetic simulations based on the calculated activation energies of the arenium cation mechanism predict that intermediates will not accumulate; this is supported by mass balance experiments. Reaction optimization studies suggest that PhI(O<sub>2</sub>CCF<sub>3</sub>)<sub>2</sub>/BF<sub>3</sub>·OEt<sub>2</sub> or MoCl<sub>5</sub> are superior to FeCl<sub>3</sub> or AlCl<sub>3</sub>/CuCl<sub>2</sub>. This is a full account of our work reported partially as a communication previously (Rempala, P.; Kroulík, J.; King, B. T. <i>J. Am. </i><i>Chem. Soc.</i> <b>2004</b>, <i>126</i>, 15002−15003). Scholl reaction;mass balance experiments;Intramolecular Scholl Reaction;bond;generation;Contiguous PhenylbenzenesTwo mechanisms;arenium cation;MoCl 5;formation;FeCl 3;Reaction optimization studies;Kinetic simulations;dehydrogenation;activation energies;arenium cation mechanism;B 3LYP level 2006-07-07
    https://acs.figshare.com/articles/journal_contribution/Investigation_of_the_Mechanism_of_the_Intramolecular_Scholl_Reaction_of_Contiguous_Phenylbenzenes/3071875
10.1021/jo0526744.s001