Fluoro, Trifluoromethyl, and Trifluoroacetyl Substituent Effects on Cycloaddition Reactivities: Computations and Analysis
Fluoro, Trifluoromethyl, and Trifluoroacetyl Substituent Effects on Cycloaddition Reactivities: Computations and Analysis
复制标题
氟、三氟甲基和三氟乙酰基取代基对环加成反应活性的影响：计算和分析
DOI：
10.1021/acs.joc.2c02264
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Liu, Fang
中科院分区：
文献类型：
--
作者：
Su, Ruirui;Xie, Kaili;Liang, Yong;Houk, K. N.;Liu, Fang
氟和三氟甲基取代基在药物有效性中的重要性促使在有价值的合成环加成中含氟取代基的计算探索。用密度泛函理论（M06-2X）研究了典型反应物环戊二烯、N-苯基重氮乙酰胺、四嗪和N-苯基悉尼酮与含氟取代基（F、CF 3和COCF 3）的Diels-Alder或1，3-偶极环加成反应.诱导效应和共轭效应对正向和反向需电反应的影响不同。这些结果为合成过程中引入氟和三氟甲基取代基的环加成反应的设计和使用提供了指导。
The importance of fluoro and trifluoromethyl substituents in drug effectiveness prompted the computational exploration of fluorine-containing substituents in valuable synthetic cycloadditions. Diels–Alder or 1,3-dipolar cycloaddition reactions of typical reactants, cyclopentadiene,N-phenyldiazoacetamide, tetrazine, andN-phenylsydnone involving fluorine-containing substituents (F, CF3, and COCF3) were studied with M06-2X density functional theory. Inductive and conjugative effects influence normal and inverse electron-demand reactions differently. These results provide a guide to the design and use of cycloadditions for the introduction of fluoro and trifluoromethyl substituents in synthetic processes.