Esterification of Carboxylic Acids with Difluoromethyl Diazomethane and Interrupted Esterification with Trifluoromethyl Diazomethane: A Fluorine Effect

• DOI: 10.1021/acs.orglett.7b02866
• Publication Date: 2017-10-05T19:23:58Z
• Authors: Shan-Qing Peng; Xiao-Wei Zhang; Long Zhang; Xiang-Guo Hu
• Keywords: Diazomethane; Fluorine

It is demonstrated that difluoromethyl diazomethane (HCF2CHN2) can react with a broad range of carboxylic acids. The reaction convenient, operationally simple, mild, and tolerant variety different functional groups. In sharp contrast, trifluoromethyl (CF3CHN2) fails to acids in most solvents, acetonitrile this reagent instead undergoes an interrupted esterification (a Mumm reaction) yield N-trifluoroethyl imides. This striking example the ability single F-for-H substitution alter pathway was rationalized through DFT study.