Selective Electrosynthesis of Biologically Active Organofluorine Compound Using a Fluorine Mediator

虽然阳极取代在有机合成中非常有用，因为它们可以一步完成，但这种取代仅限于有机氮化合物。最近，我们发现氟离子显著促进了硫基化合物的阳极取代。另一方面，由于有机氟化合物具有独特的生物活性，开发高效的选择性合成方法变得越来越重要。然而，由于氟原子的特殊性，它们的合成并不总是那么容易。从这些观点出发，我们尝试使用氟介质选择性电合成具有生物活性的有机氟化合物，如下所示。1)氟离子介导的2-甲氧基-3,3,3-三氟丙基苯基硫化物的阳极甲氧基化及其合成应用。2)用氟离子介质电合成2-乙氧羰基-3,3,3-三氟丙基苯基硫化物的-三氟甲基化O， s -缩醛和-（三氟甲基）丙烯酸酯衍生物。3)氟离子介导的2-羟基-3,3,3-三氟丙基苯基硫化物的阳极甲氧基化及其在光活性有机氟化合物合成中的应用。4)氟离子介质电合成含CF_3基团的光学活性氧硫代烷。我们已经完成了以上四个项目，并发现一些电合成产物显示出了良好的生物活性。

Although anodic substitutions are quite useful in organic synthesis since they can be done in one step, such subsitutions are limited to organic nitrogen compounds. Recently, we found that fluoride ions markedly promoted anodic substitutions of chalcogeno compounds. On the other hand, development of efficient selective synthetic methods of organofluorine compounds has been increasingly important since they have unique biological activities. However, due to specific fluorine atoms, their synthesis is not always easy.From these viewpoints, we have attempted selective electrosynthesis of biologically active organofluorine compounds using a fluorine mediator as follows.1) Fluoride ion mediated anodic alpha-methoxylation of 2-methoxy-3,3,3-trifluoropropyl phenyl sulfide and its synthetic application.2) Electrosynthesis of beta-trifluoromethylated O,S-acetal and alpha-(trifluoromethyl)acrylate derivatives from 2-ethoxycarbonyl-3,3,3-trifluoropropyl phenyl sulfide using a fluoride ion mediator.3) Fluoride ion mediated anodic alpha-methoxylation of 2-hydroxy-3,3,3-trifluoropropyl phenyl sulfide and its application to the synthesis of optically active organofluorine compounds.4) Electrosynthesis of optically active oxathiolanes having a CF_3 group using a fluoride ion mediator.We have acieved above four projects and found that some of electrosynthsized products show maked biological activities.