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，前列腺素的新的实用和有效的合成是非常重要的。本文所述的新方法构成以下新工艺。(1)以二价阴离子衍生的琥珀酸酯为原料，构建五元环体系的新方法。(2)合作阻断效应的发现和利用这种效应的不对称Diels-Alder反应产生了高光学纯度的六元环系统。(3)一些加合物转化为前列腺素衍生物，发现其具有高度生物活性。(4)具有酒石酸酯配体的丙二烯基硼酸酯被证明对于前列腺素衍生物的侧链的构建是非常有用的。(5)不对称环丙烷化反应新工艺成功地应用于前列腺素类似物的合成，这些合成方法不仅适用于前列腺素衍生物，而且可广泛应用于各种生物活性物质。

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。”

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。”

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。