Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
J Am Chem Soc. 2012 Jun 27;134(25):10401-4. doi: 10.1021/ja3048255. Epub 2012 Jun 14.
Although fluorinated compounds have found widespread applications in the chemical and materials industries, general and site-specific C(sp(3))-F bond formations are still a challenging task. We report here that with the catalysis of AgNO(3), various aliphatic carboxylic acids undergo efficient decarboxylative fluorination with SELECTFLUOR(®) reagent in aqueous solution, leading to the synthesis of the corresponding alkyl fluorides in satisfactory yields under mild conditions. This radical fluorination method is not only efficient and general but also chemoselective and functional-group-compatible, thus making it highly practical in the synthesis of fluorinated molecules. A mechanism involvinig Ag(III)-mediated single electron transfer followed by fluorine atom transfer is proposed for this catalytic fluorodecarboxylation.
虽然氟化合物在化学和材料工业中得到了广泛的应用，但普遍存在的 C(sp(3))-F 键的形成仍然是一项具有挑战性的任务。我们在这里报告，在 AgNO(3)的催化下，各种脂肪族羧酸在水溶液中与 SELECTFLUOR(®)试剂发生有效的脱羧氟化反应，在温和条件下以令人满意的收率得到相应的烷基氟化物。这种自由基氟化方法不仅高效、通用，而且具有选择性和官能团兼容性，因此在氟化分子的合成中具有很高的实用性。提出了一种涉及 Ag(III)介导的单电子转移，然后是氟原子转移的催化脱羧氟化反应机制。
