Synthesis, Properties, and Reactivity of (1 H ,1 H -Perfluoroalkyl)- and (1 H -Perfluoro-1-alkenyl)aryliodonium Triflates and Their Analogs

Abstract

(1H,1H-Perfluoroalkyl)phenyl- and -(p-fluorophenyl)iodoniurn triflates, fluorosulfate, sulfate (3)–(7) were synthesized in good yields by the oxidation of 1-iodo-1H,1H-perfluoroalkanes (RfCH2I) with trifluoroperacetic acid followed by treatment with triflic acid and benzene or fluorobenzene. (1H,1H,5H,5H-Perfluoropentane-1,5-diyl)bisphenylbisiodonium triflate was synthesized similarly. (trans-1H-Perfluoro-1-alkenyl)phenyliodonium triflates (11) were synthesized by dehydrofluorination of 3 with a base in good yields. Thermolysis of 3 produced 1H,1H-perfluoroalkyl triflate and iodobenzene, while 11 gave (Z)-1-iodo-1H-perfluoro-1-alkene and phenyl triflate. The thermolysis experiment, including (perfluoroalkyl)phenyliodonium triflate (17), demonstrated that the C–I bond strength of the trivalent iodine compounds increased in the order of RfCH2–I, Rf–I