An Energetic Guide for Estimating Trifluoromethyl Cation Donor Abilities of Electrophilic Trifluoromethylating Reagents: Computations of X–CF3 Bond Heterolytic Dissociation Enthalpies,The Journal of Organic Chemistry

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An Energetic Guide for Estimating Trifluoromethyl Cation Donor Abilities of Electrophilic Trifluoromethylating Reagents: Computations of X–CF3 Bond Heterolytic Dissociation Enthalpies
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2016-03-31 00:00:00 , DOI: 10.1021/acs.joc.5b02821
Man Li , Xiao-Song Xue , Jinping Guo , Ya Wang , Jin-Pei Cheng ₁

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This work established an energetic guide for estimating the trifluoromethyl cation-donating abilities (TC⁺DA) of electrophilic trifluoromethylating reagents through computing X–CF₃ bond (X = O, S, Se, Te, and I) heterolytic dissociation enthalpies. TC⁺DA values for a wide range of popular reagents were derived on the basis of density functional calculations (M06-2X). A good correspondence has been identified between the computed TC⁺DA values and the experimentally observed relative trifluoromethylating capabilities of the reagents. Substituent effects hold good linear free energy relationships on the TC⁺DAs of the most widely used reagents including Umemoto reagent, Yagupolskii–Umemoto reagent, and Togni reagents, which allow their trifluoromethylating capabilities to be rationally tuned by substituents and thus extend their synthetic utility. All the information disclosed in this work would contribute to future rational exploration of the electrophilic trifluoromethylation chemistry.

中文翻译：

估算亲电子三氟甲基化试剂三氟甲基阳离子供体能力的能量指南：X–CF ₃键杂分解解焓的计算

这项工作为通过计算X–CF ₃键（X = O，S，Se，Te和I）杂解离解焓来估算亲电子三氟甲基化试剂的三氟甲基阳离子给体能力（TC ⁺ DA）提供了有力的指导。多种常用试剂的TC ⁺ DA值是根据密度泛函计算（M06-2X）得出的。在计算出的TC ⁺ DA值与实验观察到的试剂的相对三氟甲基化能力之间已经确定了良好的对应关系。取代基效应在TC ⁺上具有良好的线性自由能关系最广泛使用的试剂的DAs，包括梅本试剂，Yagupolskii-梅梅试剂和Togni试剂，可以通过取代基合理地调节其三氟甲基化能力，从而扩展了其合成用途。在这项工作中公开的所有信息将有助于对亲电三氟甲基化化学的未来合理探索。

更新日期：2016-03-31

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