Development of Industrial Synthetic Process Toward Prostaglandins

前列腺素工业合成工艺的发展

• 批准号: 60850154
• 负责人: YAMAMOTO Hisashi
• 金额: $ 4.86万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60850154/
• 关键词: Prostaglandin; Dianion; Asymmetric Diels-Alder; Allenyl Anion; 不斉シクロプロパン化; 不斉Diels-Alder; 不斉合成

New practical and efficient synthesis of prostaglandin is highly important both from biological as well as synthetic point of view. The new methods described herein constitute the following new process.(1) A new process for the construction of five-membered ring system starting from the dianion derived succinate esters. (2) Discovery of cooperative blocking effect and utilization of this effect for the asymmetric Diels-Alder reaction produced the six-membered ring system of high optical purities. (3) some of the adducts was transformed to the prostaglandin derivative which is found to be biologically highly active. (4) Allenylboronic ester with tartaric ester ligands was shown to be quite useful for the construction of the side chain of prostaglandin derivatives. (5) a new process of asymmetric cyclopropanation reaction successfully applied for the preparation of prostaglandin analogs.These synthetic methods are not only useful for the prostaglandin derivatives but also could be applied broadly in a wide variety of biologically active substances.

从生物学和合成的角度来看，前列腺素的新实用和有效合成非常重要。本文所述的新方法构成了以下新过程。（1）从dianion衍生的琥珀酸酯酯开始构建五元环系统的新过程。 （2）发现合作阻塞效应和这种对不对称的Diels-Alder反应的利用产生了高光学纯度的六元环系统。 （3）某些加合物被转化为前列腺素衍生物，该衍生物被认为具有生物学上的活性。 （4）具有tart酯配体的甲烯基晶体酯被证明对构造前列腺素衍生物的侧链非常有用。 （5）成功地应用了前列腺素类似物的新的不对称环丙谁反应的新过程。这些合成方法不仅对前列腺素衍生物有用，而且可以广泛地应用于多种生物学活性物质中。

项目成果

Kyoji Furuta: "Asymmetric Diels-Alder Reaction. Cooperative Blocking Effect in Organic Synthesis." Tetrahedron Lett.,. 27. 4507-4510 (1986)

Kyoji Furuta：“不对称狄尔斯-阿尔德反应。有机合成中的协同阻断效应。”

Hisashi Yamamoto: "Asymmetric Synthesis Using Main Group Organometallic Reagents." Workshop Conferences Hoechst,. 17. 13-29 (1987)

Hisashi Yamamoto：“使用主族有机金属试剂进行不对称合成。”

Hisashi Yamamoto: "Chiralsynthon? -Homochiral Acetal in Organic Synthesis.-" J. Synthetic Organic Chemistry, Japan. 45. 944-956 (1987)

Hisashi Yamamoto：“Chiralsynthon？-有机合成中的同手性乙缩醛。-”J.合成有机化学，日本。

山本尚: 旭硝子工業技術奨励会研究報告. 50. 9-20 (1987)

山本隆：旭硝子工业技术振兴协会研究报告 50. 9-20 (1987)。

Isao Arai: "An Asymmetric Simmons-Smith Reaction." J. Am. Chem. Soc.,. 107. 8254-8256 (1985)

Isao Arai：“不对称的西蒙斯-史密斯反应。”