Site-Selective C–H Mono- and Bis-Thianthrenation of Polycyclic Aromatic Hydrocarbons

Organic functional materials are often constructed from polycyclic aromatic hydrocarbons. They contain multiple C–H positions making site-selective functionalization challenging. We present the highly site-selective thianthrenation of unsubstituted polycyclic aromatic hydrocarbons giving single regioisomers. The site-selectivity was computationally rationalized using DFT methods. Bis-thianthrenation was achieved on biphenyl and azulene, with structures confirmed by single-crystal X-ray diffraction. These results encourage the use of thianthrenation for the construction of building blocks for organic functional materials.