Syntheses of Biologically Active Natural Products by Intramolecular Double Michael Reaction

分子内双迈克尔反应合成生物活性天然产物

• 批准号: 62570929
• 负责人: IHARA Masataka
• 金额: $ 1.15万
• 依托单位: TOHOKU 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: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62570929/
• 关键词: Organic Synthesis; Intramolecular Double Michael Reaction; Biologically Active Natural Product; Steroid; Alkaloid; Terpene; Stereoselective Synthesis; 不斉合成; 有機合成化学; 生理活性化天然化合物; 環化反応

In orber to develop a general methodology for the stereoselectione construction of polycyclic compounds, the intramolecular double Michael reation was investigated. The objective annulation was effectively achieced by the following three different. conditions:(A)treatment with lithium amide,(B)heating with TMSCl,Et_3N,EnCl_2,(C) treament with TBSOTF and ET_3N. A Diterpene (atisirene),a diterpene alkaloid (atisine),triquinene sesquiterpenes (pentalenene, pentalenic acid and deoxypentalenic acid) and estrane type steroids were totally synthesized via the annulation under conditions(A and B). On the ther hand , syntheses of alkaloids (epilupinine and tylophorine) were accomplished through the cyclisation under the conditions (B and C). Asymmetric synthesis was also successfully carried out under the condition (C).

为了发展立体选择性构筑多环化合物的一般方法，研究了分子内双Michael反应。通过以下三种不同的方法有效地实现了目标成环。条件：（A）氨基锂处理，（B）TMSCl、Et_3N、EnCl_2加热，（C）TBSOTF和ET_3N处理。在条件（A和B）下，通过环合反应全合成了一种二萜（阿替西烯）、一种二萜生物碱（阿替辛）、三醌倍半萜（并环戊二烯、并环戊二烯酸和脱氧并环戊二烯酸）和雌甾烷型甾体化合物。另外，在（B和C）条件下，通过环合反应合成了生物碱（Epilupinine和Eschophorine）。在条件（C）下也成功地进行了不对称合成。

项目成果

井原正隆: J.Am.Chem.Soc.110. 1963-1964 (1988)

伊原正孝：J.Am.Chem.Soc.110 1963-1964 (1988)。

M.Ihara: "Stereoselective Total Synthesis of ( )- Atisine via Intramolecular Double Michael Reaction" J. Am. Chem. Soc.110. 1963-1964 (1988)

M.Ihara：“通过分子内双迈克尔反应立体选择性全合成 ( )- Atisine” J. Am.

井原正隆: J.Chem.Soc,Chem.Commun.1467-1468 (1987)

井原正孝：J.Chem.Soc,Chem.Commun.1467-1468 (1987)

井原正隆: J.Chem.Soc.,Perkin Trans.l. 1155-1163 (1988)

井原正孝：J.Chem.Soc.，Perkin Trans.l. 1155-1163 (1988)

M.Ihara: "Total Synthesis of ( )-Pentalenic Acid via Intramolecular Double Michael Reaction." J. Chem. Soc. Chem. Commun.721-722 (1987)

M.Ihara：“通过分子内双迈克尔反应全合成 ( )-戊烯酸。”