Development of General Synthetic Method for Bicyclic Compounds by Reductive Cyclization Reactions Using SmI_2

SmI_2还原环化双环化合物通用合成方法的发展

• 批准号: 13672245
• 负责人: MOTOO Tori
• 金额: $ 1.98万
• 依托单位: Tokushima Bunri University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13672245/
• 关键词: SmI_2; cyclization; reduction; stereochemistry; bicyclic compound; hydrindanone; perhydronaphthalenone; perhydroazulenone; ペルヒドロナフタレン

This work aims at establishing a general concept of synthesizing bicyclic compounds by the reductive cyclization reaction using SmI_2. The reaction of an enone with an aldehyde in the same molecule with SmI_2 smoothly occurred to produce cyclized bicyclic ketols depending on the conditions used. When no additive was used, namely SmI_2 in THF at rt or lower temperature, products have cis relationship between a hydroxyl group and a juncture substituent. While in the presence of methanol as a proton source, a hydroxyl group and a juncture substituent have trans relationship each other. These stereochemistries were established by measuring the NOEs, performing the equilibrium experiments under basic conditions, and in some cases by X-ray crystallographic analysis. The cyclization into 6- and 7-membered rings smoothly worked in the 6-Endo-Trig or 7-Endo-Trig mode of cyclization. However, 5-membered rings were difficult to realize presumably due to the Baldwin rule. We have demonstrated the synthetic method into hydrindanones, perhydronaphtahlenones, and perhydroazulenones in good to moderate yields. This method can be applied to another type of bicyclic compounds, which is the future program in this laboratory.

本工作的目的是建立一个一般性的概念，合成双环化合物的还原环化反应使用SmI_2。在SmI_2存在下，同一分子中的一个烯酮和一个醛可以顺利地发生反应，生成环化的双环酮醇。当不使用添加剂，即SmI_2在THF中，在室温或更低温度下，产物的羟基与连接取代基之间为顺式关系。而在甲醇作为质子源存在下，羟基和连接取代基之间存在反式关系。通过测量NOE、在碱性条件下进行平衡实验以及在某些情况下通过X射线晶体学分析来建立这些立体化学。在6-Endo-Trig或7-Endo-Trig环化模式下，环化成6-和7-元环顺利进行。然而，5元环很难实现，可能是由于鲍德温规则。我们已经以良好至中等的产率证明了合成方法为氢化茚满酮、全氢化萘烯酮和全氢化甘菊环烯酮。此方法可应用于另一类双环化合物，是本实验室未来的研究方向。

项目成果

M.Sono, S.Onishi, M.Tori: "Cyclization into Perhydronaphthalenones Using Samarium Diiodide"Tetrahedron, in press. 59. (2003)

M.Sono、S.Onishi、M.Tori：“使用二碘化钐环化成全氢化萘酮”四面体，正在出版。

M. Sono, Y. Nakashiba, K. Nakashima, S. Takaoka, and M. Tori: "Samarium (II) Iodide-mediated Intramolecular Aldol-type Cyclization"Heterocycles. 54. 101-104 (2001)

M. Sono、Y. Nakashiba、K. Nakashima、S. Takaoka 和 M. Tori：“钐 (II) 碘化物介导的分子内羟醛型环化”杂环。

M.Sono, S.Onishi, M.Tori: "Cyclization into Perhydronaphthalenones Using Samarium Diiodide"Tetrahedron. in press.

M.Sono、S.Onishi、M.Tori：“使用二碘化钐环化成全氢化萘酮”四面体。

M.Sono, Y.Nakashiba, K.Nakashima, M.Tori: "Cyclization into hydrindanones using samarium diiodide"Journal of Organic Chemistry. 65,10. 3099-3106 (2000)

M.Sono、Y.Nakashiba、K.Nakashima、M.Tori：“使用二碘化钐环化为茚满酮”有机化学杂志。

M.Sono, A.Hashimoto, T.Nakashima, M.Tori: "Total synthesis of coronafacic acid through 6-endo-trig mode intramolecular cyclization of an enone-aldehyde to a hydrindanone usig samarium(II) indide"Tetrahderon Letters. 41,26. 5115-5118 (2000)

M.Sono、A.Hashimoto、T.Nakashima、M.Tori：“通过 6-endo-trig 模式分子内环化烯酮醛至茚满酮的全合成，使用钐(II) indide”Tetrahderon Letters。