Synthesis of functionalized azacalix[3]aromatics from azacalix[4]pyrimidine: unexpected macrocyclic transannular reactions

The lower-rim formylated azacalix[4]pyrimidine underwent transannular Friedel–Crafts and dehydrogenative cross coupling reactions to afford, respectively, 2,4,5,7-tetraaza-9,10-dihydroacridine and -dihydroacridin-9-one containing azacalix[3]aromatics. Dihalogenation of the later compound produced resolvable inherently chiral azacalix[3]aromatics.