Synthetic Studies on Polyquinane Sesquiterpenes

聚奎烷倍半萜的合成研究

• 批准号: 63570992
• 负责人: IMANISHI Takeshi
• 金额: $ 1.28万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63570992/
• 关键词: Natural product synthesis; Bond cleavage of cyclopronae ring; Sesquiterpene; Polyquinane; Pentalenene; Quadrone; 抗腫瘍活性; クァドロン類縁体; シクロプロパン; 全合成; 立体選択性; 制癌作用

Polyquinane framework plays an important role of structural unit of many kinds of naturally occurring organic compounds, some of which exhibit significantly biological activities. In this project, a couple of poluquinane sesquiterpenes were successfully synthesized by the use of a common intermediate 1 which was subjected to regioselective C-C bond cleavage of cyclopropane ring.The Birch reduction of 1 exclusively afforded the bicyclo 3.3.0 octane 2 via C_2-C_8 bond fission of the cyclopropane ring, while treatment of 1 under nucleophilic substitution conditions gave the bicyclo 3.2.1 octane 3 as a main product via the C_1-C_2 ond cleavage. On the other hand, the carboxylic acid 4, easily obtained from 1, afforded the lactone 5 efficiently through the exclusive C_1-C_2 bond fission by an intramolecular carboxylic acid participation.Through the several-step sequence starting from 2, total synthesis of a representative triqyinane sesquiterpene pentalenene (6) was accomplished.Descarboxyquadrone (7) and an antitumor diquinane sesquiterpene quardrone (9) were also synthesized by the use of key intermediates 3 and 8,respectively.

聚奎烷骨架在多种天然有机化合物的结构单元中发挥着重要作用，其中一些化合物表现出显着的生物活性。在该项目中，通过使用共同的中间体1，对环丙烷环进行区域选择性C-C键断裂，成功合成了几种聚奎烷倍半萜。1的Birch还原通过C_2-C_8独家得到双环3.3.0辛烷2环丙烷环的键裂变，而在亲核取代条件下处理1得到双环3.2.1辛烷3作为C_1-C_2二次裂解的主要产物。另一方面，由1容易获得的羧酸4通过分子内羧酸参与的排他性C_1-C_2键裂变有效地提供了内酯5。通过从2开始的几个步骤序列，全合成了具有代表性的内酯5。完成了三喹烷倍半萜五烯 (6)。去羧基四氢呋喃 (7) 和抗肿瘤二奎烷倍半萜还分别使用关键中间体3和8合成了夸酮(9)。

项目成果

Takeshi Imanishi et al.: "7,7-Dimethyltricyclo[3.3.0.0^]octan-3-ones as Synthetic Intermediates.V.An Improved Synthesis of(±)-Pentalenene" Chem.Pharm.Bull.38. (1990)

Takeshi Imanishi 等人：“7,7-二甲基三环[3.3.0.0^<2,8>]octan-3-ones 作为合成中间体。V.(±)-Pentalenene 的改进合成”Chem.Pharm.Bull。 38. (1990)

Takeshi Imanishi, Masayuki Yamashita, Munetaka Matsui, Tetsuaki Tanaka, and Chuzo Iwata: "----- III. Total Synthesis of ()-Descarboxyquadro " Chem. Pharm. Bull., 36, 2012-2016, 1988.

Takeshi Imanishi、Masayuki Yamashita、Munetaka Matsui、Tetsuaki Tanaka 和 Chuzo Iwata：“----- III. (<plus-minus>)-Descarboxyquadro 的全合成” Chem。

Takeshi Imanishi et al.: "7,7ーDimethy1tricyclo[3.3.0.0^]octanー3ーones as Synthetic Intermediates.II.a Total Synthesis of(±)ーPentalenene,an Angular Triquinane Sesquiterpene" Chem.Pharm.Bull.36. 1371-1378 (1988)

Takeshi Imanishi 等人：“7,7－二甲基1三环[3.3.0.0^<2,8>]辛烷－3－酮作为合成中间体。II.a 全合成(±)－Pentalenene,an Angular Triquinane Sesquiterpene” .Pharm.Bull.36。1371-1378 (1988)

Takeshi Imanishi: Chem.Pharm.Bull.36. 1351-1357 (1988)

今西武：Chem.Pharm.Bull.36。

Takeshi Imanishi et al.: "7,7-Dimethyltricyclo[3.3.0.0^]octan-3-ones as Synthetic Intermediates.II.A Total Synthesis of(±)-Pentalenene,Angular Triquinane Sesquiterpene" Chem.Pharm.Bull.36. 1371-1378 (1988)

Takeshi Imanishi 等人：“7,7-二甲基三环[3.3.0.0^<2,8>]octan-3-ones 作为合成中间体。II.(±)-Pentalenene、Angular Triquinane Sesquiterpene 的全合成” Chem。药学公报.36。1371-1378 (1988)