Selective alternate derivatization of the hexaphenylbenzene framework through a thermodynamically controlled halogen dance.

We report a practical synthetic protocol and mechanistic details for the selective alternate derivatization of the hexaphenylbenzene (HPB) framework through a thermodynamically controlled halogen dance. The stability of the alternately trilithiated species of HPB is interpreted by the through-space interaction at the ipso-carbons of the phenyl groups of the HPB framework. By using this approach, C3-symmetric and lower-symmetric HPB derivatives possessing two or three kinds of substituents on the periphery have become easily and practically available.