Peripherally Arylated 2,8-Diazaperylenes from Anthracene Diimide: Synthesis and Oxidative Annulation.

We have synthesized 1,3,7,9-tetrapivaloxy-2,8-diazaperylene through reductive aromatization of anthracene diimide in the presence of zinc powder and pivalic anhydride. The pivaloxy groups were readily converted to aryl groups through nickel-catalyzed cross-coupling reaction with arylboronic acids. Introduction of the nitrogen atoms imparts acid responsiveness to the perylene skeleton, resulting significant changes in its photophysical properties. Oxidative annulation of the peripheral aryl groups with bay positions of the diazaperylene core provided 2,10-diazadibenzocoronenes in good yields.