Development of Novel Asymmetric Fluorination Using Electrolysis

利用电解开发新型不对称氟化

• 批准号: 11650885
• 负责人: FUCHIGAMI Toshio
• 金额: $ 2.37万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650885/
• 关键词: Asymmetric Fluorination; Anodic Fluorination; Trifluorinated Sulfide; Thiazolidine; Selective Fluorination; Chiral Auxiliary; Chiral Fluoroorganics; Diastereoselective Fluorination; 電解不斉フッ素化; 分子内不斉誘導; ジアステレオ選択性; α-フェニルチオ酢酸エステル; 超音波電解; 電解フッ素化

Chiral organofluorine compounds are highly useful for medicines, agrochemicals, and functional materials. Optical resolution, biological and chiral fluorobuilding block methods have been mainly employed so far. Asymmetric fluorination seems to be the mostideal method for the preparation of chiral organofluorine compounds. However, studies on asymmetric fluorination have been limited and there have been few successful examples.On the other hand, we have recently developed versatile selective anodic fluorination of organic compounds.With these in mind, asymmetric anodic fluorination using various chiral induction methods has been attempted as follows :1) Diastereoselective Anodic Fluorination of Thiazolidines2) Highly Diastereoselective Anodic Fluorination of 3, 3, 3-Trifluoro-2-methoxypropyl Sulfides3) Diastereoselective Anodic Fluorination of a-Phenylthioacetates Having Chiral AuxiliariesWe have achieved above three projects and the results obtained in these projects would be highly useful for further studies on asymmetric anodic fluorination of various organic molecules.

手性有机氟化合物在医药、农用化学品和功能材料方面非常有用。迄今为止主要采用光学拆分、生物和手性氟砌块方法。不对称氟化似乎是制备手性有机氟化合物最理想的方法。然而，关于不对称氟化的研究有限，成功的例子也很少。另一方面，我们最近开发了多功能的有机化合物选择性阳极氟化。考虑到这些，使用各种手性诱导方法的不对称阳极氟化已经尝试如下：1）噻唑烷的非对映选择性阳极氟化2）高度非对映选择性阳极氟化 3, 3, 3-三氟-2-甲氧基丙基硫醚的制备3) 具有手性助剂的α-苯硫代乙酸酯的非对映选择性阳极氟化我们已经完成了上述三个项目，这些项目中获得的结果对于进一步研究各种有机分子的不对称阳极氟化非常有用。

项目成果

S'ayed M.Riyad: "Highly Regioselective Anodic Mono-and Difluorination of Propargyl Sulfides and Preparation of α-Fluoroallenyl Sulfides"Tetrahedron Letters. 42.(印刷中). (2001)

Sayed M.Riyad：“炔丙基硫醚的高度区域选择性阳极单氟化和二氟化以及 α-氟丙二烯硫醚的制备”四面体快报 42（印刷中）。

渕上寿雄: "フッ素系生理活性物質の進歩と応用展開-電解フッ素化法"シーエムシー. 15 (2000)

Hisao Fuchigami：“氟化生理活性物质的进展和应用开发-电解氟化法”CMC 15（2000）。

T.Fuchigami: ""Electrochemical Fluorination Method" in "Development of Fluorinated Biologically Active Compounds" ed. T.Taguchi"CMC, Tokyo. 54-68 (2000)

T.Fuchigami：“氟化生物活性化合物的开发”中的“电化学氟化方法”，T.Taguchi 编辑”CMC，东京。

淵上寿雄: "最新電極触媒の科学"北海道大学図書刊行会. 15 (2001)

Hisao Fuchigami：“电催化剂的最新科学”北海道大学图书出版协会15（2001）。

Kamal M.Dawood: "Anodic Fluorination of 2-Pyrimidyl,2-Pyridyl,and 2-Quinazolinonyl Sulfides"Journal of Organic Chemistry. 64・21. 7935-7939 (1999)

Kamal M.Dawood：“2-嘧啶基、2-吡啶基和2-喹唑啉基硫化物的阳极氟化”有机化学杂志64・21（1999）。