Studies on the Development of Innovative Approaches for A Highly Stereocontrolled Construction of Structurally Diverse Fluoroalkene Skeletons

• Material Type: 博士論文
• Title: Studies on the Development of Innovative Approaches for A Highly Stereocontrolled Construction of Structurally Diverse Fluoroalkene Skeletons
• Author/Editor: Nihei, Takashi
• Author Heading: Nihei, Takashi
• Publication Date: 2015-03-25
• Publication Date (W3CDTF): 2015-03-25
• Alternative Title: 多様なフルオロアルケン骨格の高位体選択的構築のための革新的な合成手法の開発に関する研究
• Degree grantor/type: 京都工芸繊維大学
• Date Granted: 2015-03-25
• Dissertation Number: 甲第732号
• Degree Type: 博士（工学）
• Text Language Code: eng
• Subject Heading: Fluoroalkenes; β-Fluoroallyl alcohol derivatives; Carbon-fluorine bond activation; Chromium(II) chloride; Regio- and stereoselective hydrostannation; Ring-opening reaction; gem-Difluorocyclopropylstannane; SN2’ reaction; β-Fluoroallyl phosphates; Regioselective ring-closing metathesis; Organocopper reagent
• Target Audience: 一般
• Note (General): type:Thesis; This thesis consists of five chapters. In Chapter 1 is referred the importance of fluoroalkene skeletons, together with general physical/chemical properties and availability of organofluorine compounds. In addition, precedent synthetic methods for the preparation of fluoroalkenes are presented. Chapter 2 describes an efficient chromium(II)-mediated reductive coupling reaction of various bromodifluoromethyl-containing molecules with aldehydes. It was revealed that the reaction proceeded very smoothly to afford the corresponding β-fluoroallylic alcohols in a highly stereoselective manner. It is particularly worth noting that (E)-β-fluoroallylic alcohols were exclusively given in the case of 3-(3-bromo-3,3-difluoropropanoyl)-2-oxazolidinone as a substrate, while (Z)-β-fluoroallylic alcohols were provided in the case of other substrates, such as 4-bromo-4,4-difluorobutylate, 3-bromo-3,3-difluoropropyl ether, and 1-bromo-1,1-difluoro-nonanes. Chapter 3 describes the unusual ring-opening reaction of gem-difluorocyclopropylstannanes, which were prepared via the radical hydrostannation of various gem-difluorocyclopropenes with n-Bu3SnH. Thus, on treating gem-difluorocyclopropylstannanes with MeLi, followed by quenching the reaction with various media, such as H2O, alcohols, carboxylic acids, and p-toluenesulfonamide, gave the corresponding β-fluoroallylic alcohols, ethers, esters, and amide in a highly Z-selective manner. Chapter 4 describes SN2’ substitution of β-fluoroallyl phosphates with organocopper reagents. It should be noted that various types of β-fluoroallyl phosphates reacted smoothly with various organoalkylcuprates, prepared from Grignard reagents, organolithium, organozinc reagents and CuCN, the corresponding terminal fluoroalkenes being obtained in a highly regioselective manner. Among thus obtained fluoroalkenes, fluorinated 1,7-dienes underwent a smooth ring-closing metathesis under the influence of Grubbs catalyst, providing the corresponding fluorinated cyclohexenes in high yields. In Chapter 5 is summarized the discussion in each chapter.
• Format (IMT): application/pdf
• Source: fulltext; http://repository.lib.kit.ac.jp/repo/repository/10212/2252/D1-0732_h1.pdf; http://repository.lib.kit.ac.jp/repo/repository/10212/2252/D1-0732.pdf
• Access Restrictions: インターネット公開
• Data Provider (Database): 国立情報学研究所 : 学術機関リポジトリデータベース（IRDB）（機関リポジトリ）; https://irdb.nii.ac.jp
• Original Data Provider (Database): 京都工芸繊維大学 : ＫＩＴ学術成果コレクション