Palladium-catalyzed intramolecular arylation provides bowl-shaped azaindenocorannulenes 7-9. Crystals of 8 show bowl-in-bowl columnar stacking. A substituent model rationalizes the first reduction potential of 18 related molecular bowls. The absolute configurations of bowls 7 and 9 are correlated with VCD and ECD spectra. The bowl inversion barrier of 9 (>190 kJ/mol) shows it to be more inert configurationally than chiral biaryl, phosphenes, or [ n]helicenes.