Aryl Thianthrenium Triflates

image A [ 195072‐48‐1 ] C 19 H 13 F 3 O 3 S 3 (MW 442.48) InChI = 1S/C18H13S2.CHF3O3S/c1‐2‐8‐14(9‐3‐1)20‐17‐12‐6‐4‐10‐15(17)19‐16‐11‐5‐7‐13‐18(16)20;2‐1(3,4)8(5,6)7/h1‐13H;(H,5,6,7)/q+1;/p‐1 InChiKey = ILICKJZOLUIMMN‐UHFFFAOYSA‐M B [ 2839478‐51‐0 ] C 20 H 14 ClF 3 O 4 S 3 (MW 506.95) InChI = 1S/C19H14ClOS2.CHF3O3S/c1‐21‐15‐11‐10‐13(12‐14(15)20)23‐18‐8‐4‐2‐6‐16(18)22‐17‐7‐3‐5‐9‐19(17)23;2‐1(3,4)8(5,6)7/h2‐12H,1H3;(H,5,6,7)/q+1;/p‐1 InChiKey = UHXRBIHFIKXURP‐UHFFFAOYSA‐M C [ 2786722‐96‐9 ] C 20 H 12 F 6 O 3 S 3 (MW 510.48) InChI = 1S/C19H12F3S2.CHF3O3S/c20‐19(21,22)13‐9‐11‐14(12‐10‐13)24‐17‐7‐3‐1‐5‐15(17)23‐16‐6‐2‐4‐8‐18(16)24;2‐1(3,4)8(5,6)7/h1‐12H;(H,5,6,7)/q+1;/p‐1 InChiKey = UEAVFAKSNUECER‐UHFFFAOYSA‐M D [ 2786723‐55‐3 ] C 18 H 12 F 3 NO 3 S 3 (MW 443.47) InChI = 1S/C17H12NS2.CHF3O3S/c1‐3‐7‐16‐14(5‐1)19‐15‐6‐2‐4‐8‐17(15)20(16)13‐9‐11‐18‐12‐10‐13;2‐1(3,4)8(5,6)7/h1‐12H;(H,5,6,7)/q+1;/p‐1 InChiKey = SRMXRMTYQFMLCQ‐UHFFFAOYSA‐M (reagents used as an aryl pseudohalide in transition‐metal catalyzed, transition metal‐free, and photochemical reactions) Physical Data : A mp 202.8–204.7 °C. 1 B mp 159.2–162.7 °C. 2 C mp (Not reported). D mp (Not reported). A–D Solubility : soluble in acetonitrile and dichloromethane. A – D Form Supplied in : not commercially available; free‐flowing solids prepared by literature procedures. 3–5 A – D Analysis of Reagent Purity : 1 H and 19 F NMR. A – D Purification : trituration from dichloromethane using diethyl ether or hexanes; silica gel chromatography (eluting with DCM:MeOH). A – D Handling, Storage, and Precautions : stable under ambient conditions for extended periods of time. 3 Can be weighed in normal atmosphere and stored in a vial under air. Preparative Methods : (From simple arenes) A Treatment of thianthrene S ‐oxide (TTSO) with trifluoroacetic anhydride (TFAA) and triflic acid (TfOH) in the presence of a desired arene in acetonitrile at 0 °C. After the addition of all reagents, reactions are typically allowed to stir between 1 and 18 h depending on the substrate. Alternatively, treatment of TTSO with triflic anhydride (Tf 2 O) in the presence of a desired arene in dichloromethane or acetonitrile at −40 °C. 3,5 After completion, the purple reaction is quenched with methanol to generate a colorless/yellow solution. The crude reaction mixture is concentrated under reduced pressure and the residue is triturated with diethyl ether to afford a solid which is isolated by filtration. A–D (From arylboronic acids) Treatment of the desired arylboronic acid with thianthrene, copper(II) triflate and water in acetonitrile under nitrogen atmosphere at 100 °C for 3 h. After aqueous workup, the crude residue is triturated with diethyl ether to afford a solid which is isolated by filtration. 4