We then explored the scope of accessible arene-and heteroarene-containing compounds under optimized conditions (Figure 3, top). For one, Ar-SF4Cl starting materials containing benzene rings -either unsubstituted or substituted with electron-withdrawing groups -provided the desired addition products 6-8 in good yields. Moreover, starting materials containing pyridine rings with various halogen (9-11), cyano (12), ester (13), trifluoromethyl (14), and nitro (15) substituents performed generally well under specified conditions. Additionally, the scope includes examples of pyrimidine-containing products, such as 16 and 17 -the latter formed in 97% yield by F NMR and isolated in 84%. During these studies, we noted that pyridine-and pyrimidine-based products of all substitution patterns were generally less prone to decomposition during attempted purification than benzene-based products without a strong electron withdrawing substituent present (e.g., a nitro )-1.6336 (7) 88.10(4)-91.29( ) o 1.8123 (18) 1.7648 (14) 1.8119 (12) 1.8386 (13) 1.6213(6)-1.6371(6) 88.68(4)-91.21(3) group), though we noted some exceptions (6 and 7). This phenomenon is in accord with what has been observed previously in compounds containing the Ar-SF4 moiety, and we have indicated a few examples of compounds in our Supporting Information where decomposition on silica gel was particularly problematic, in contrast to the entries shown in Figure .