Developments of Novel Synthetic Reactions under High Pressure Conditions

高压条件下新型合成反应的进展

• 批准号: 05453063
• 负责人: KOTSUKI Hiyoshizo
• 金额: $ 4.8万
• 依托单位: Kochi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453063/
• 关键词: High Pressure Reaction; Silica Gel Catalyzed Reaction; Aminolysis; Epoxide Opening Reaction; Heterocyclic Compounds; Chiral Ligands; Halohydrin; Functionalized Silica Gel; 有機合成; シリカゲル; エポキシド; キラル配位子; ジオールマイシン; 酒石酸; 超分子化合物; Diels-Alder反応; 樹

(a) Diels-Alder Reaction of Resin Acids : Novel Diels-Alder reaction of methyl palustrate with maleic anhydride and N-phenylmaleimide has been established under high pressure conditions.(b) Synthetic Study of AI-77-B : High pressure approach to construct the amide bond between a dihydroisocoumarin and a hydroxyamino acid part of AI-77-B has been investigated. Thus, as a model reaction, the N-Boc lactam derivative prepared from D-ribose was efficiently condensed with cyclohexylamine at 10 kbar pressure without using any catalysis.(c) Aminolysis of Epoxides with Glycine Esters : Uncatalyzed aminolysis of epoxides with glycine esters has been efficiently performed under high pressure conditions. In connection with this study, we found that silica gel acted as a powerful solid acid catalyst for this type of epoxide opening reaction.(d) Reaction of Epoxides with Nitrogen Heterocycles : The reaction of epoxides with nitrogen heterocycles such as indoles, pyrroles, and pyrazoles has been perf … More ormed under high pressure-promoted or silica gel-catalyzed conditions. The stereochemical feature for an epoxide opening reaction with indole has been proposed as having a concerted S_N2 mechanism.(e) Synthetic Design of Novel Chiral Ligands : High pressure reaction of chiral epoxides with pyrazoles provided novel procedure to obtain chiral diazole ligands. These ligands were successfully applied for an enantioselective alkylation of benzaldehyde with diethylzinc.(f) Synthesis of Diolmycin A2 : A new short synthesis of diolmycin A2 has been performed by using high pressure-promoted epoxide opening reaction with indole as a key step.(g) Transformation of epoxides to the Corresponding Halohydrins : A variety of epoxides have been efficiently converted into the corresponding halohydrins by treatment with silica gel-supported lithium halides in dry media.(h) Functionalization of Silica Gel under High Pressure Conditions : As a final project to use high pressurt chemistry, a new method to functionalize silica gel with chiral substances has been developed and its utility for HPLC analysis has been also demonstrated. Less

(a)树脂酸的Diels-Alder反应：在高压条件下，建立了新的Palustate甲酯与马来酸酐和N-苯基马来酰亚胺的Diels-Alder反应。(b)AI-77-B的合成研究：研究了在二氢异香豆素和AI-77-B的羟基氨基酸部分之间构建酰胺键的高压方法。因此，作为模型反应，由D-核糖制备的N-Boc内酰胺衍生物与环己胺在10千巴压力下有效地缩合而不使用任何催化剂。(c)环氧化合物与甘氨酸酯的氨解：环氧化合物与甘氨酸酯的非催化氨解在高压条件下有效地进行。在这项研究中，我们发现，硅胶作为一个强大的固体酸催化剂，这种类型的环氧化物开环反应。(d)环氧化物与氮杂环的反应：环氧化物与氮杂环如吲哚，吡咯和吡唑的反应已经被进行了。 ...更多信息 在高压促进或硅胶催化条件下形成。吲哚开环反应的立体化学特征为S_N2协同机理。(e)新型手性配体的合成设计：手性环氧化物与吡唑类化合物的高压反应为合成手性二唑类配体提供了新的途径。这些配体成功地应用于苯甲醛与二乙基锌的不对称烷基化反应。(f)迪奥霉素A2的合成：采用高压促进的吲哚环氧化物开环反应作为关键步骤，进行了迪奥霉素A2的新的短合成。(g)将环氧化物转化为相应的卤代醇：通过在干燥介质中用硅胶负载的卤化锂处理，多种环氧化物已被有效地转化为相应的卤代醇。(h)高压条件下硅胶的功能化：作为使用高压化学的最终项目，开发了一种用手性物质功能化硅胶的新方法，并证明了其在HPLC分析中的实用性。少

项目成果

Hiyoshizo Kotsuki: "High Pressure Organic Chemistry, X1X, HIgh Pressure Promoted, Sirica-Gel Catalyzed Reaction of Epoxides with Nitrogen Heterocycles" Journal of Organic Chemistry. 61. (1996)

Hiyoshizo Kotsuki：“高压有机化学，X1X，高压促进，Sirica-凝胶催化环氧化物与氮杂环的反应”有机化学杂志。

H.Kotsuki: "A New Concise Approach to the Enantioselective Synthesis of the Hydroxyamino Acid Moiety of AI-77-B" Heterocycles. 38. 17-20 (1994)

H.Kotsuki：“AI-77-B 羟基氨基酸部分的对映选择性合成的新简明方法”杂环。

H.Kotsuki: "A New Facile Conversion of Epoxides to β-Halohydrins with Silica Gel-Supported Lithium Halides" Gedrahedron Letters. 37(印刷中). (1996)

H. Kotsuki：“用硅胶支持的卤化锂将环氧化物轻松转化为 β-卤代醇”，Gedrahedron Letters 37（出版中）。

H.Kotsuki: "Synthesis of Novel Chiral Diazole Ligands for Enantioselective Addition of Diethylzinc to Benzaldehyde" Tetrahedron : Asymmetry. 6. 2665-2668 (1995)

H.Kotsuki：“用于二乙基锌与苯甲醛对映选择性加成的新型手性二唑配体的合成”四面体：不对称性。

H.Kotsuki: "A Facile Conversion of Epoxides to beta-Halohydrins with Silica Gel-Supported Lithium Halides" Tetrahedron Lett.(in press.).

H.Kotsuki：“用硅胶支持的卤化锂将环氧化物轻松转化为 β-卤代醇”Tetrahedron Lett.（正在印刷中）。