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Structure-dependent selective O- or C-trifluoroethylation of 1,3-dicarbonyls by mesityl(2,2,2-trifluoroethyl)iodonium triflate
Journal of Fluorine Chemistry ( IF 1.9 ) Pub Date : 2017-09-22 , DOI: 10.1016/j.jfluchem.2017.09.009
Cheng-Long Zhao , Jing Yang , Zhou-Zhou Han , Cheng-Pan Zhang

Reaction of [ArICH2CF3][OTf] with structurally diversified 1,3-dicarbonyls and an appropriate base at room temperature gave O-trifluoroethylated products, C-trifluoroethylated products, or a mixture of O- and C-trifluoroethylated products in good yields. The product type was dramatically dependent upon the structure of the starting 1,3-dicarbonyls in this reaction. The cyclic 1,3-diketones exclusively afforded the O-trifluoroethylated products, whereas the acyclic 1,3-diketones, β-keto esters, and malonates selectively or specifically formed the C-trifluoroethylated products. Li2CO3 facilitated the C-trifluoroethylation of acyclic 1,3-diketones and β-keto esters. The reaction proceeded under mild conditions, without pre-activation of 1,3-dicarbonyls and use of strong base, and demonstrated a catalyst-free structure-dependent regioselective trifluoroethylation of 1,3-dicarbonyls by mesityl(2,2,2-trifluoroethyl)iodonium triflate.



中文翻译:

1,3,2-二羰基三氟甲磺酸碘鎓盐对1,3-二羰基的结构依赖性选择性O-C-三氟乙基化

[ArICH 2 CF 3 ] [OTf]与结构上多样化的1,3-二羰基化合物和适当的碱在室温下反应,生成的O-三氟乙基化产物,C-三氟乙基化产物或O-C-三氟乙基化产物的混合物产量。产物类型极大地取决于该反应中起始的1,3-二羰基的结构。环状的1,3-二酮专门提供了O-三氟乙基化产物,而无环的1,3-二酮,β-酮酯和丙二酸酯选择性地或特异性地形成了C-三氟乙基化产物。李2CO 3促进了无环1,3-二酮和β-酮酯的C-三氟乙基化。该反应在温和的条件下进行,没有预活化1,3-二羰基化合物和使用强碱,并且证明了1,3,2-二羰基的无催化剂依赖性的区域选择性三氟乙基化是由1,3,2-二羰基组成的。三氟甲磺酸碘

更新日期:2017-09-22
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