Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide
Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide
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DOI：
10.1002/ejoc.201800551
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发表时间：
2018-08-01
影响因子：
2.8
通讯作者：
Iskra, Jernej
中科院分区：
文献类型：
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作者：
Horvat, Monika;Jereb, Marjan;Iskra, Jernej
研究了在三氟甲磺酸催化下，芳香族化合物与不同的ArNHSCF_3型亲电试剂的三氟甲基硫醇化反应。用三种不同的试剂PhNHSCF_3（H/SCF_3，1a），4-ClC_6 H_4 NHSCF_3（Cl/SCF_3，1b）和C_6 F_5 NHSCF_3（F-5/SCF_3，1c）研究了试剂结构对反应活性的影响。对氯取代的试剂1b比未取代的试剂1a更稳定，并且是最有效的，因为它不能通过自身的三氟甲基硫醇化反应。该反应是1a最重要的副反应。五氟衍生物1c的反应性较低。溶剂在转化中起重要作用，并且根据底物，二氯甲烷、己烷或三氟乙酸给出各种三氟甲基硫醇化的芳族分子的最佳产率（63-98%）。
Trifluoromethylthiolation of aromatic compounds with different electrophilic reagents of the type ArNHSCF3 was studied in the presence of triflic acid as an activator. The effect of the reagent structure on the reactivity was studied with three different reagents: PhNHSCF3 (H/SCF3, 1a), 4-ClC6H4NHSCF3 (Cl/SCF3, 1b) and C6F5NHSCF3 (F-5/SCF3, 1c). p-Chloro substituted reagent 1b was more stable than the unsubstituted 1a and was the most effective because it could not react by trifluoromethylthiolation of itself. This reaction was the most important side reaction of 1a. The pentafluoro derivative 1c was less reactive. Solvent played an important role in the transformation and, depending on the substrate, dichloromethane, hexane or trifluoroacetic acid gave the best yield of various trifluoromethylthiolated aromatic molecules (63-98%).