Here we report the use of the hexadehydro-Diels-Alder (HDDA) reaction for the de novo construction of a benzenoid ring in fused polycyclic heteroaromatic carbazole (i.e., [2,3]-benzoindole) skeletons. The strategy allows creation of highly substituted benzenoids. We also describe the HDDA-enabled chemical synthesis of the natural product alkaloids mahanimbine and koenidine. Trapping of the intermediate carbazolyne with a conjugated enal, proceeding through formal [2+2] cycloaddition, 4 pi-electrocyclic ring opening, and 6 pi-electrocyclic ring-closing events, constitutes a robust method for producing pyranocarbazoles.