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Effective Preparation of Valuable Biologically Active Compounds Employing Catalytic Construction of Polycyclic Ring System

利用多环体系催化构建有效制备有价值的生物活性化合物

基本信息

批准号：
17390003
负责人：
IHARA Masataka
金额：
$ 9.47万
依托单位：
Hoshi University (2006)Tohoku University (2005)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

When various functional groups exist on a polycyclic skeleton, the three-dimensional relationships of the functional groups are restricted and a specific biological activity would be expected due to the rigid conformation. Therefore, the development of an efficient method for the construction of polycyclic ring systems is highly desired, particularly in the field of medicinal chemistry.Cascade reactions are useful methods for the construction of polycyclic skeletons, which are important cores for biological activities. A variety of cascade reactions, carried out under multiple reaction conditions, such as pericyclic, polar, radical, and transition metal-catalyzed reaction conditions, have been investigated.Culmorin, pentalenene, pentalenic acid, deoxypentalenic acid, longiborneol, cedrandiol, 8, 14-cedranoxide, atisirene, atisine, and estrane-type steroids were synthesized via the intramolecular double Michael reaction. Aza double Michael reaction was applied to the syntheses of tylophorine, epilupinine, tacamonine, and paroxetine. Furthermore, sequential Michael and aldol reactions were performed in both intramolecular and intermolecular manners, leading to the formation of polycyclic compounds fused to a four-membered ring. Synthesis of paesslerin A utilizing a multicomponent cascade reaction revealed an error in the proposed structure.Unique cascade reactions, performed under radical and transition metal-catalyzed reaction conditions, were also investigated. With the combination of several cascade reactions, serofendic acids and methyl 7β-hydroxykaurenoate, both of which have neuroprotective activity, were synthesized in a selective manner.

当多环骨架上存在各种官能团时，官能团的三维关系受到限制，并且由于刚性构象而预期特定的生物活性。因此，在药物化学领域，人们迫切需要开发一种有效的多环骨架的构建方法，而多环骨架是生物活性的重要核心，级联反应是构建多环骨架的有效方法。本论文研究了在多反应条件下（如周环反应、极性反应、自由基反应、过渡金属催化反应等）的分子内双Michael反应，合成了Culmorin、pentalenene、pentalenic acid、deoxypentalenic acid、longioline、cedrandiol、8，14-cedranoxide、atisirene、atisine和雌甾烷型甾体化合物。应用氮杂双Michael反应合成了三尖杉碱、Epilupinine、他坎必特和帕罗西汀。此外，连续的迈克尔和羟醛缩合反应进行分子内和分子间的方式，导致形成稠合到一个四元环的多环化合物。利用多组分级联反应合成paesslerin A揭示了一个错误的结构。独特的级联反应，进行自由基和过渡金属催化的反应条件下，也进行了研究。通过几个级联反应的组合，以选择性的方式合成了具有神经保护活性的血清芬酸和7β-羟基贝壳杉烯酸甲酯。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Palladium-catalyzed carbon dioxide elimination-fixation reaction of 6-methoxycarbonyloxy-2, 4-hexadien-1-ols.

钯催化的 6-甲氧基羰氧基-2, 4-己二烯-1-醇的二氧化碳消除固定反应。

DOI：
发表时间：
2006
期刊：
Tetrahedron 62
影响因子：
0
作者：
Kazato Inanaga;Kiyosei Takasu;Masataka Ihara;Kiyosei Takasu 他2名;Kiyosei Takasu 他3名;Kiyosei Takasu 他6名;Kiyosei Takasu 他4名;Yamagishi K.;Yamagishi K.;Masahiro Yoshida;Masahiro Yoshida;Masahiro Yoshida
通讯作者：
Masahiro Yoshida

Synthesis of Medium-Sized Cyclic γ-Haloketones by Radical Mediated Ring-Opening Reaction of Lewis Acid of Lewis Acid Catalyzed(2+2)-Cycloaddition Product

路易斯酸催化(2+2)-环加成产物自由基介导的路易斯酸开环反应合成中型环状γ-卤代酮