Preparation and Utilization of Chiral Building Blocks Having Bicyclo[2.2.1]heptane Ring System

双环[2.2.1]庚烷环系手性砌块的制备及应用

• 批准号: 03453152
• 负责人: TAKANO Seiichi
• 金额: $ 4.29万
• 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 (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453152/
• 关键词: Chiral building block; Chiral cyclopentadienone synthon; Chiral cyclohexadienone synthon; Chiral bicyclo[2.2.1]heptane system; Lipase-mediated resolution; Enantiomerization; Asymmetrization of mesomer; Retro-Diels-Alder Cleavage; キラルシクロペンタジエノン素子 /

Two chiral building blocks having bicyclo[2.2.1]heptane ring system have been prepared by employing lipase mediated resolution as the key step. Namely, optically pure ketodicyclopentadiene serving as chiral equivalent of cyclopentadienone was prepared from dicyclopentadiene by empoying either lipase mediated asymmetric esterification or deacylation reaction. An efficient procedure for the enantiomerization has also been established. On the other hand, optically pure homoketodicyclopentadiene serving as chiral equivalent of cyclohexadienone was prepared in both enatiomeric forms from the Diels-Alder adduct of p-benzoquinone and cyclopentadiene by asymmetrization via the lipase-mediated enantiospecific mono-esterification of the meso-symmetric intermediate.Based on molecular bias of these componds owing to the bicyclo[2.2.1]heptane ring system and facile retro-Diels-Alder removal of cyclopentadiene, a variety of physiologically active natural products ranging from a simple monoterpene to a complex polyoxygenated plant toxin have been synthesized in a complete stereocontrolled way.

通过采用脂肪酶介导的分辨率作为关键步骤，已经制备了两个具有二烷环系统的手性构件[2.2.1]。也就是说，通过对脂肪酶介导的不对称酯化或脱酰基化反应，从双环戊二烯制备了光学上的酮环丙烯，用作环戊烯酮的手性等效。还建立了对映体化的有效程序。另一方面，光学纯的纯种环丙烯是在两种表面上用p-苯二喹酮的Diels-Alder加合物中的同性恋形式制备的，是在两种环己二烯的手势上，并通过通过lipase介导的元素化构造单体化合物 - 偶联性单层化的膜化合物，并通过不对称化的膜化。这些偏差构成了由于Bicyclo [2.2.1]的heptane环系统和柔和的retro-Diels-Alder拆除环戊烷的去除，因此，各种生理活性的天然产品从简单的单萜到复杂的多氧化植物毒素的范围都在完整的Stereoconconconconconconconconconconconconconeldeconconed May中被合成。

项目成果

Seiichi Takano: "Non-Hazardous Preparation of Acetoxy- and Keto-Dicyclopentadienes" Synthesis. 印刷中.

Seiichi Takano：“乙酰氧基和酮基二环戊二烯的无害制备”合成正在出版。

Seiichi Takano: "Non-Hazardous Preparation of Acetoxy- and Ketodicyclopentadienes Synthesis" in press.

Seiichi Takano：“乙酰氧基和酮二环戊二烯合成的无危险制备”正在出版。

Seiichi Takano: "A Concise Enantiocontrolled Total Synthesis of (+)-Estrone" Tetrahedron Lett.33. 1909-1910 (1992)

Seiichi Takano：“( )-Estrone 的简明对映体控制全合成”四面体 Lett.33。

Seiichi Takano: "Enantiocontrolled Sysnthesis of Optically Pure 5-Trimethylsilyl- and 5-Tributylstannylcyclohex-2-enones" J.Chem. Soc., Chem. Commun.788-789 (1993)

Seiichi Takano：“光学纯 5-三甲基甲硅烷基-和 5-三丁基甲锡烷基环己-2-烯酮的对映体控制合成”J.Chem。

Seiichi Takano: "Enantiodivergent Route to Conductoriol C via Lipase-Mediated Asymmetrization" J.Chem. Soc., Chem. Commun.177-178 (1993)

Seiichi Takano：“通过脂肪酶介导的不对称化实现Conductoriol C 的对映异构路线”J.Chem。