Efficient Synthesis of Symmetrically and Unsymmetrically Substituted Hexaphenylbenzene Analogues by Suzuki–Miyaura Coupling Reactions

A series of symmetrically and unsymmetrically substituted hexaphenylbenzene (HPB) analogues were efficiently synthesized by using a sterically hindered Suzuki–Miyaura cross‐coupling reaction of arylboronic acids with 1,4‐diiodo‐2,3,5,6‐tetraarylbenzenes under our optimized reaction conditions. The 1,4‐diiodo‐2,3,5,6‐tetraarylbenzenes can be readily prepared by using a one‐pot Hart reaction. Oxidative cyclodehydrogenation of the dibromo derivative with FeCl₃ gave the corresponding hexabenzocoronene (HBC) derivative in good yield.