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 in the construction of building blocks for organic functional materials.