Annulated corannulenes 3-5 form via distinct synthetic pathways: (i) Pd-catalyzed sp3 CH insertion, (ii) Pd-catalyzed aryl coupling, and (iii) silyl cation-promoted C-F activation/CH insertion. Crystal structure, redox, and photophysical studies elucidate the differing influence of 1,2,3- versus 1,2-indeno ring fusions. Mono and dianions of 3-5 are characterized. Resolution of 4 gives enantiopure forms, allowing assessment of the bowl-inversion barrier.