Bertrand Xavier, Pucheault Mathieu, Chabaud Laurent, Paquin Jean-François
CCVC, PROTEO, Département de chimie, Université Laval, 1045 Avenue de la médecine, Québec, Québec G1V 0A6, Canada.
Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400 Talence, France.
J Org Chem. 2023 Oct 20;88(20):14527-14539. doi: 10.1021/acs.joc.3c01558. Epub 2023 Sep 28.
The combination of methanesulfonic acid and potassium bifluoride is reported for the deoxyfluorination of tertiary alcohols. Under metal-free conditions that use readily available, cheap, and easy-to-handle reagents, a range of tertiary alcohols could be converted into the corresponding fluorides in excellent yields (average yields of 85% for 23 examples). Mechanistic investigation showed that the reaction proceeds at 0 °C, in part, through an elimination/hydrofluorination pathway, but no residual alkenes are observed. The application of these conditions for the fluorination of ether and ester is also demonstrated.
据报道，甲磺酸和氟化氢钾的组合可用于叔醇的脱氧氟化反应。在无金属条件下，使用易于获得、廉价且易于操作的试剂，一系列叔醇可以以优异的产率（23个实例的平均产率为85%）转化为相应的氟化物。机理研究表明，该反应在0℃下部分通过消除/氢氟化途径进行，但未观察到残留的烯烃。还展示了这些条件在醚和酯氟化反应中的应用。
