Aryl thianthrenium salts are linchpin reagents for latestage C-H functionalization reactions. These reagents typically participate in metal-catalyzed reaction, but are also compatible with photo-redox catalysis. Installation of the thianthrenium group is guided by the existing arene substituents and the ultimate functionalization event occurs by ipso-substitution of the thianthrenium leaving group, including the formation of C-N bonds (Scheme 5a, top). 10d Conversely, we leverage the deprotonation of aryl thianthrenium to generate an aryne intermediate with two electrophilic sites (Scheme 5a, bottom). Nucleophilic attack on arynes is guided by the existing substituents and offers the possibility of complimentary functionalization. For instance, methoxy groups guide distal attack on the aryne therefore resulting in overall cine-substitution (Scheme 5a, bottom). We have obtained experimental validation for this selectivity and demonstrated that C-H amination from 1d occurs meta to the methoxy group via the aryne intermediate. Both morpholine and aniline are compatible nucleophiles in this case (Scheme 5b). The overall yield of 3e in the formal dehydrogenation/aryne hydroamination is 67% from arene 1d (Scheme 5b). Additionally, the two-step yield of 3f when aniline is used as nucleophile is 86% from 1d (Scheme 5b). Notably, other recent reports of C-H amination on 1d, and related substrates, that do not involve thianthrenium occur ortho to the methoxy group, 18a,h,q and therefore our approach with aryne intermediates offers a complementary strategy for C-H amination of electron-rich arenes. We are further exploring the novel selectivity of nucleophilic addition with substituted anisole derivatives as the aryne precursor and the synthetic possibilities that emerge. Scheme 5. Selective C-H amination enabled by aryne intermediate.