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首页> 外文期刊>Chemistry: A European journal >S-Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study
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S-Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study

机译：高价碘试剂对硫醇进行S-三氟甲基化：联合实验和计算研究

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摘要

The radical trifluoromethylation of thiophenol in condensed phase applying reagent 1 (3,3-dimethyl-1-(trifluoromethyl)-1 lambda(3), 2-benziodoxol) has been examined by both theoretical and experimental methodologies. On the basis of ab initio molecular dynamics and metadynamics we show that radical reaction mechanisms favourably compete with polar ones involving the S-centred nucleophile thiophenol, their free energies of activation, Delta F-not equal, lying between 9 and 15 kcal mol(-1). We further show that the origin of the proton activating the reagent is important. Hammett plot analysis reveals intramolecular protonation of 1, thus generating negative charge on the sulfur atom in the rate-determining step. The formation of a CF3 radical can be thermally induced by internal dissociative electron transfer, its activation energy, Delta F-not equal, amounting to as little as 10.8 and 2.8 kcal mol(-1) for reagent 1 and its protonated form 2, respectively. The reduction of the iodine atom by thiophenol occurs either subsequently or in a concerted fashion.
机译：已通过理论和实验方法研究了苯酚在缩合相中应用试剂1（3,3-二甲基-1-（三氟甲基）-1 lambda（3），2-benziodoxol）的自由基三氟甲基化。根据从头算的分子动力学和元动力学，我们表明自由基反应机理可与涉及S中心亲核试剂苯硫酚的极性反应机理竞争，其活化能为Delta F-不相等，介于9至15 kcal mol（- 1）。我们进一步表明，质子活化试剂的起源很重要。哈米特图分析显示分子内质子为1，因此在速率确定步骤中在硫原子上产生负电荷。 CF3自由基的形成可以由内部解离电子转移热诱导，其活化能Delta F-不相等，对于试剂1及其质子化形式2分别低至10.8和2.8 kcal mol（-1）。 。硫酚对碘原子的还原随后发生或以一致的方式发生。

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