Fluoroarenes bearing no electron-withdrawing groups (non-activated fluoroarenes) readily underwent nucleophilic aromatic substitution with α-cyanocarbanions under microwave irradiation. The sequence (i) formylalkylation involving the cyanoalkylation of fluoroarenes, (ii) difluorovinylidenation, and (iii) Friedel-Crafts-type cyclization, afforded extended fluoroarenes by one benzene ring per cycle. Furthermore, the performance of multiple cycles successfully provided higher-order pinpoint-fluorinated polycyclic aromatic hydrocarbons (F-PAHs).

Lords of the Rings: Owing to the electronic and steric impacts of fluorine substituents, pinpoint‐fluorinated polycyclic aromatic hydrocarbons (PAHs) are promising organic semiconductors that might result in printable organic electronic devices. In this study, the development of an aromatic ring extension cycle that allows transformation of fluoroarenes into extended fluoroarenes by one benzene ring per cycle is reported. The synthesis of pinpoint‐fluorinated picene, having five benzene rings was successfully demonstrated by performing multiple cycles starting from commercially available 1‐fluoronaphthalene. More information can be found in the Communication by Kohei Fuchibe, Hisanori Imaoka, and Junji Ichikawa on page 2359 in Issue 18, 2017 (DOI:10.1002/asia.201700870).