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Development of New Photo-, Electric-, and Molecular-Devised Materials Using High Pressure Technology

利用高压技术开发新型光、电和分子设计材料

基本信息

批准号：
09554047
负责人：
KOTSUKI Hiyoshizo
金额：
$ 7.74万
依托单位：
Kochi University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09554047/
关键词：
Michael Addition Reaction Nitrogen Heterocycles Quinazoline Derivatives Silica Gel Supports Natural Products Synthesis Chiral Columns Epoxide Opening Reaction High Pressure Condensation ホモ共役付加反応 AI-77-B キラルピリジンキナゾリンシリカゲルキラルカラム

项目摘要

(a) Michael Addition Reactions of β-Ketoesters : Michael addition reactions of β-ketoesters with a variety of α, β-unsaturated carbonyl compounds using Yb(OTf)ィイD23ィエD2 / SiOィイD22ィエD2 or TfOH under solvent-free conditions have been established. In addition, homo-Michael addition reaction using activated cyclopropane derivatives has been achieved at high pressure.(b) Asymmetric Catalysis Using Novel Nitrogen Heterocycles : Several chiral dipyridine and dithiophene derived ligands for the use in the catalytic enantioselective alkylation have been developed.(c) Synthesis of Quinazoline Compounds : A variety of quinazoline derivatives have been prepared by condensation of cyano- and nitro-activated o-fluorobenzaldehydes with amidines in good yields.(d) Supported Reactions on Silica Gel : Solvent-free organic reactions on silica gel supports have been developed: transformation of epoxides to halohydrins using LiX / SiOィイD22ィエD2 and chemoselective deprotection of N-Boc carboxamides using Yb(OTf)ィイD23ィエD2/ SiOィイD22ィエD2.(e) Natural Product Synthesis : An enantioselective total synthesis of AI-77-B, a gastroprotective substance isolated from a culture broth of Bacillus pumilus AI-77, has been performed in high overall yield.(f) Molecular Template Formation Using High Pressure Technique : Molecular template formation of bovine serum albumin-silica gels under high pressure conditions and its use for chiral HPLC analysis have been performed.(g) Functional Group Transfonnations : Chemoselective reductive transformation of azides to N-Boc protected amines , Sc(OTf)ィイD23ィエD2- or TfOH-catalyzed Baeyer-Villiger oxidation and high-pressure-promoted LiClO)ィイD24ィエD2 -catalyzed reaction of epoxides with furans or thiophenes .

(a) β-酮酯的迈克尔加成反应：已经建立了在无溶剂条件下使用 Yb(OTf)ィイD23ィエD2 / SiOィイD22ィエD2 或 TfOH β-酮酯与各种 α, β-不饱和羰基化合物的迈克尔加成反应。此外，在高压下实现了使用活化环丙烷衍生物的均迈克尔加成反应。(b)使用新型氮杂环的不对称催化：开发了几种用于催化对映选择性烷基化的手性二吡啶和二噻吩衍生配体。(c)喹唑啉化合物的合成：各种喹唑啉通过氰基和硝基活化的邻氟苯甲醛与脒的缩合，以良好的收率制备了衍生物。(d) 硅胶上的支持反应：已开发出硅胶支持上的无溶剂有机反应：使用 LiX / SiOiiD22ィeD2 将环氧化物转化为卤代醇，并对 N-Boc 进行化学选择性脱保护使用 Yb(OTf)ィイD23ィエD2/ SiOィイD22ィエD2 合成甲酰胺。(e) 天然产物合成：AI-77-B（一种从短小芽孢杆菌 AI-77 培养液中分离出来的胃保护物质）的对映选择性全合成已实现高总产率。(f) 使用高压技术形成分子模板: 分子模板高压条件下牛血清白蛋白-硅胶的形成及其在手性 HPLC 分析中的应用。(g) 官能团转换：叠氮化物化学选择性还原转化为 N-Boc 保护的胺，Sc(OTf)ィイD23ィD2- 或 TfOH 催化的 Baeyer-Villiger 氧化和高压促进 LiClO)ィイD24ィエD2 - 催化环氧化物与呋喃或噻吩的反应。