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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具有特定的生物活性。因此，特别是在药物化学领域，迫切需要开发一种有效的多环体系构建方法。级联反应是构建多环骨架的有用方法，而多环骨架是生物活性的重要核心。研究了在周环、极性、自由基、过渡金属催化等多种反应条件下进行的多种级联反应，合成了Culmorin、并环戊烯烯、戊烯酸、脱氧戊烯酸、长冰片、柏木二醇、8, 14-柏木氧化物、阿替西林、阿替辛和雌烷类固醇通过分子内双迈克尔反应。氮杂双Michael反应被应用于tylophorine、epilupinine、tacamonine和paroxetine的合成。此外，连续的迈克尔和羟醛反应以分子内和分子间的方式进行，导致形成稠合到四元环的多环化合物。利用多组分级联反应合成 Paesslerin A 揭示了所提出的结构中的错误。还研究了在自由基和过渡金属催化反应条件下进行的独特级联反应。通过多个级联反应的结合，选择性合成了具有神经保护活性的丝罗芬酸和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