Development of New Stereoselective Reaction and its Application

新型立体选择性反应的进展及其应用

• 批准号: 62470133
• 负责人: SHIBASAKI Masakatsu
• 金额: $ 4.93万
• 依托单位: Hokkaido 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: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62470133/
• 关键词: Silyl Dienol Ether; Prostacyclin Derivative; Beta-Lactam; Cr(CO)_3 Complex; Copper Triflate; Isomerization Reaction; β-ラクタム; クロムカルボニル錯体; コッパ-トリフレ-ト; 抗潰瘍剤; エノールエーテル; シリルジエノールエーテル; クロムトリカルボニル錯体; カルバペネム抗生物質; ペネム抗生物質; プロスはサイクリン誘導体

We have succeeded in development of the new stereoselective reactions and their application to the synthesis of biologically important compounds as follows.1. The stereocontrolled synthesis of aryl-substituted exocyclic olefins has been achieved for the first time by utilizing naphthalene・Cr (CO)_3 catalyzed isomerization of conjugated dienes as a key step.2. The stereocontrolled synthesis of silyl dienol ethers having E, Z-configurations has been achieved for the first time by utilizing naphthalene・Cr (CO)_3 catalyzed isomerization of conjugated dienes.3. A highly efficient synthesis of antiulcer nileprost has been achieved by utilizing reduction-isomerization reaction of the conjugated dienes.4. Cu (I) OTf has been found to be an extremely useful reagent for the synthesis of beta-lactams from beta-amino thiol esters.5. The eastern part of azadirachtin has been synthesized starting with malic acid.6. A catalytic asymmetric synthesis of cis-decalin derivatives has been achieved by utilizing Heck-type reaction of prochiral alkenyl iodides.

我们已经成功地开发了新的立体选择性反应及其在合成生物重要化合物中的应用如下。以萘·Cr（CO）_3催化共轭二烯异构化反应为关键步骤，首次实现了芳基取代环外烯烃的立体控制合成.利用萘·Cr（CO）_3催化共轭双烯异构化反应，首次实现了E，Z构型硅基双烯醇醚的立体控制合成.利用共轭二烯的还原-异构化反应，实现了抗溃疡药物尼勒前列素的高效合成.已发现Cu（I）OTf是用于从β-氨基硫醇酯合成β-内酰胺的极其有用的试剂。5.印楝素的东部是以苹果酸为起始原料合成的。利用前手性烯基碘的Heck反应实现了顺式十氢萘衍生物的催化不对称合成。

项目成果

高橋敦男: J.Am.Chim.Soc.

高桥敦夫：J.Am.Chim.Soc。

M.Sodeoka,H.Yamada and M.Shibasaki: "New Method for Sterecontrolled Synthesis of Silyl Dienol Ethers Using Naphthlene Chromium Tricarbonyl Catalyzed Isomerization" J.Am.Chem.Soc.(1990)

M.Sodeoka、H.Yamada 和 M.Shibasaki：“利用萘铬三羰基催化异构化立体控制合成甲硅烷基二烯醇醚的新方法”J.Am.Chem.Soc.(1990)

A. Takahashi, Y. Kirio, M. Sodeoka, H. Sasai, and M. Shibasaki: "Highly Stereoselective Synthesis of Exocyclic Tetrasubstituted Enol Ethers and Olefins. A Synthesis of Nileprost" J. Am. Chem. Soc.111. 643-647 (1989)

A. Takahashi、Y. Kirio、M. Sodeoka、H. Sasai 和 M. Shibasaki：“环外四取代烯醇醚和烯烃的高度立体选择性合成。尼罗前列素的合成”J. Am。

Y.Sato,M.Sodeoka,and M.Shibasaki: "Catalytic Asymmetric C-C Bond Formation:Asymmetric Synthesis of cis-Decalin Derivatives by Palladium-Catalyzed Cyclization of Prochiral Alkenyl Iodides" J.Org.Chem.,. 54. 4738-4739 (1989)

Y.Sato、M.Sodeoka 和 M.Shibasaki：“催化不对称 C-C 键形成：通过钯催化环化前手性烯基碘化物不对称合成顺式十氢化萘衍生物”J.Org.Chem.,。

A.Takahashi,C.Yamamoto and M.Shibasaki: "A Highly Stereoselective Synthesis of Methoxycarbonyl-Substituted Exocyclic Inol Ethers:A Synthesis of 5-Methoxycarbonylprostacyclin" Heterocycles. 30. 617-626 (1990)

A.Takahashi、C.Yamamoto 和 M.Shibasaki：“甲氧基羰基取代的环外醇醚的高度立体选择性合成：5-甲氧基羰基前列环素的合成”杂环。