Development of Novel Organic Fine Chemicals based on Polycycles

基于多环的新型有机精细化学品的开发

• 批准号: 02555174
• 负责人: EGUCHI Shoji
• 金额: $ 8.13万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02555174/
• 关键词: Azahomoadamant-4-ene; Nitrone; Iminophosphorane; Quinazoline alkaloid; Cyclonucleoside; Reductive ring-enlargement; 2, 2'-Anhydrothymine; Trifluoromethyl group; クラウンエーテル; トリフルオロアセチル基; 1,3-ジケトン; 縮合型ピラゾール; アラビノシル誘導体; 3-ホモアダマンテン; 1,3-双極性環化付加反応

In this project, design and synthesis of some selected carbo- and heteropolycycles have been carried out in order to develop novel organic fine chemicals for industrial use based on polycycles like adamantane. The results can be summarized as follows :1) A bridge-imine, 4-azahomoadamant-4-ene obtainable readily from adamantane was converted to the corresponding N-oxide, i.e., a novel bridged nitrone, which was shown to be useful intermediate for synthesis of homoadamantano [4,5] fused heterocycles such as isooxazolidines, isooxazolines, and pyrroles etc.2) A short-step synthesis of quinazoline alkaloids, Rutecarpine and Tryptanthrin has been developed via intramolecular aza-Wittig methodology. A novel route to polyazamacrocycles has been developed via quinazolinone-annelation of lactams, followed by reductive ring-enlargement.3) A cyclonucleoside, 2,2'-anhydrothymine derivative was shown to be useful inter-mediate for biologically important 3'-substituted arabinonucleosides.4) A facile synthesis of beta-chloro-beta-trifluoromethyl DELTA^<alpha,beta>-carbonyl compounds has been developed by using transition metal-induced coupling reaction. Also a novel route to indole skeletons via [4+2] cycloaddition reaction of acetyl pyrrole derivatives has been developed. These compounds are expected as useful synthetic blocks for bioactive compounds.

本项目设计合成了一些碳环和杂多环化合物，以开发基于金刚烷等多环化合物的新型有机精细化工产品。1）将可容易地从金刚烷获得的桥亚胺4-氮杂高金刚烷-4-烯转化为相应的N-氧化物，即，2）采用分子内aza-Wittig方法，一步合成了喹唑啉类生物碱、芸香碱和色胺酮。通过喹唑啉酮与内酰胺的缩合反应，再还原扩环，得到了一种新的多氮杂大环化合物; 3）环己基糖苷2，2 ′-脱水胸腺嘧啶衍生物是合成具有重要生物活性的3 ′-取代阿拉伯糖苷的有效中间体; 4）通过过渡金属诱导的偶联反应合成了β-氯-β-三氟甲基Δ ^<α，β>-羰基化合物。同时还发展了一条通过乙酰基吡咯衍生物的[4+2]环加成反应合成吲哚骨架的新途径。这些化合物有望作为生物活性化合物的有用合成嵌段。

项目成果

Shoji Eguchi: "The Aza-Witting Reaction in Heterocyclic Synthesis" Org.Prep.and Proced.Int.,. 24(4). 209-243 (1992)

Shoji Eguchi：“杂环合成中的 Aza-Witting 反应”Org.Prep.and Proced.Int.，。

Yang YU: "Synthesis of 4-Azahomoadamant-4-ene N-Oxides and Their 1,3-Dipolar Cycloaddtion Reactivity" Tetrahedron letters. 32. 4965-4968 (1991)

于阳：“4-Azahomoadamant-4-ene N-氧化物的合成及其1,3-偶极环加成反应性”四面体字母。

Takashi OKANO: "Ruthenium(II)ーCatalyzed Trifluorochloropropylidenation of Silyl Enol Ethers.A Facile Method for the Preparation of TrifluoromethylーContaining Carbonyl Compounds" Synlett. 403-404 (1990)

Takashi OKANO：“钌(II)——催化的甲硅烷基烯醇醚的三氟氯丙叉化反应。一种制备三氟甲基的羰基化合物的简单方法”Synlett 403-404 (1990)。

Hisato TAKEUCHI: "Novel Ring Enlargement of Lactams via Quinazolinone Annelation.Facile Route to Benzoannelated LargeーMembered Cyclic 1,5ーDiamines" Journal of Organic Chemistry. 56. 1535-1537 (1991)

Hisato TAKEUCHI：“通过喹唑啉酮退火实现内酰胺的新型扩环。苯并大分子环状 1,5-二胺的简易路线”有机化学杂志 56. 1535-1537 (1991)。

Takashi Okano: "Ruthenium (II)-Catalyzed Trifluorochloropropyl-idenation of Silyl Enol Ethers. A Facile Method for Preparatin of Trifluoromethyl-containing Carbonyl Compounds" Synlett. (7). 403-404 (1990)

Takashi Okano：“钌 (II) 催化的硅烯醇醚的三氟氯丙基化。一种制备含三氟甲基的羰基化合物的简便方法”Synlett。