Understanding Polyarene Trifluoromethylation with Hot CF3 Radicals Using Corannulene

New insights into the process of high‐temperature trifluoromethylation of polycyclic aromatic hydrocarbons (PAHs) were gained in a detailed study of the reactions between corannulene (C20H10) and CF3I gas. Ten new poly(trifluoromethyl)corannulenes were made in these reactions and were fully characterized. A detailed computational study explains the observed trends in the product distribution and why some products cannot be prepared even with an excess of the reagent gas. The approach utilized here may have good predictive value for designing new effective and selective synthetic methodologies for various thermally stable electron‐deficient PAHs. Finding the balance between cost and benefit: Drastic energy increase when CF3 groups add to peri‐ and ortho positions on the corannulene rim explains the observed relative distribution of corannulene(CF3)n products in high‐temperature radical trifluoromethylation reactions.