Selective Electrosynthesis of Biologically Active Organofluorine Compound Using a Fluorine Mediator

使用氟介体选择性电合成生物活性有机氟化合物

• 批准号: 09650949
• 负责人: FUCHIGAMI Toshio
• 金额: $ 2.11万
• 依托单位: TOKYO INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650949/
• 关键词: Stereoselective synthesis; Mediator; Biologically active compound; Anodic substitution; Anodic cycliation; Organofluorine compound; Oxathiolane; Chiral compound; 光学活性オキサチオラン; 光学活性スルフィド; 光学活性トリフルオロメチル化合物; 含フッ素化合物; 電解メトキシ化; 電解合成; 1,2不斎誘導

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.

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，开发高效的有机氟化合物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很容易。从这些观点出发，我们尝试了以下几种具有生物活性的有机氟化合物的选择性电合成：1)氟离子介导的2-甲氧基-3，3，3-三氟丙基苯硫醚的阳极α-甲氧基化反应及其合成应用；2)2-三氟甲基-3，3，3-三氟丙基苯硫醚的β-三氟甲基化O，S缩醛和α-(三氟甲基)丙烯酸酯的电合成3-三氟丙基苯硫醚及其在合成光学活性有机氟化合物中的应用。4)以氟离子为介体，电合成具有CF3基团的光学活性氧硫杂环戊烷。

项目成果

淵上 寿雄: "環境にやさしい有機電解合成" フアルマシア. 34. 1118-1122 (1998)

Hisao Fuchigami：“环境友好的有机电合成”Pharmacia 34. 1118-1122 (1998)。

渕上寿雄: "Advances in Electron Transfer Chemistry.Vol.6" JAI Press, 90 (1999)

Hisao Fuchigami：“电子转移化学进展.Vol.6”JAI Press，90（1999）

T.Fuchigami: "Enviromentary Friendly Electroorganic Synthesis" Pharmacia. 34. 1118-1122 (1998)

T.Fuchigami：“环境友好的有机电合成”法玛西亚。

渕上 寿雄: "Adrances in Electron Transfer Chemistry" JAI Press, (1998)

Hisao Fuchigami：“电子转移化学的进展”JAI Press，（1998）

古田昇二: "Fluoride Ion Mediated Anodic α-Methoxylation of 2-Methoxy-3, 3, 3-trifluoropproyl phenyl Sulfide an Its Synthetic Application" Electrochimica Acta. 43. 3153-3157 (1998)

Shoji Furuta：“氟离子介导的 2-甲氧基-3, 3, 3-三氟丙酰基苯基硫醚的阳极 α-甲氧基化及其合成应用” 电化学学报 43. 3153-3157 (1998)