Esterification of Carboxylic Acids with Difluoromethyl Diazomethane and Interrupted Esterification with Trifluoromethyl Diazomethane: A Fluorine Effect
Esterification of Carboxylic Acids with Difluoromethyl Diazomethane and Interrupted Esterification with Trifluoromethyl Diazomethane: A Fluorine Effect
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羧酸与二氟甲基重氮甲烷的酯化反应和与三氟甲基重氮甲烷的间断酯化反应：氟效应
DOI：
10.1021/acs.orglett.7b02866
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发表时间：
2017
期刊：
影响因子：
5.2
通讯作者：
Hu Xiang-Guo
中科院分区：
文献类型：
--
作者：
Peng Shan-Qing;Zhang Xiao-Wei;Zhang Long;Hu Xiang-Guo
研究表明，二氟甲基重氮甲烷（HCF_2CHN_2）可与多种羧酸反应。该反应是方便的，操作简单，温和，并容忍各种不同的官能团。与此形成鲜明对比的是，三氟甲基重氮甲烷（CF 3CHN 2）在大多数溶剂中不能与羧酸反应，而在乙腈中，该试剂反而经历中断的酯化（Mumm反应），生成N-三氟乙基酰亚胺。通过密度泛函理论研究，我们证明了单次F取代H改变反应途径的能力。
It is demonstrated that difluoromethyl diazomethane (HCF2CHN2) can react with a broad range of carboxylic acids. The reaction is convenient, operationally simple, mild, and tolerant of a variety of different functional groups. In sharp contrast, trifluoromethyl diazomethane (CF3CHN2) fails to react with carboxylic acids in most solvents, and in acetonitrile this reagent instead undergoes an interrupted esterification (a Mumm reaction) to yieldN-trifluoroethyl imides. This striking example of the ability of a single F-for-H substitution to alter a reaction pathway was rationalized through a DFT study.