Development of Versatile Chiral Building Blocks from Meso-Enediol Compounds Utilizing Catalytic Asymmetrization Reactions

利用催化不对称反应从内消旋烯二醇化合物开发多功能手性结构单元

• 批准号: 09672134
• 负责人: HIROYA Kou
• 金额: $ 2.3万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09672134/
• 关键词: chiral building block; cationic rhodium complex; enantioselective synthesit; (-)-shikimic acid; (-)-quinic acid; (-)-zeylenol; (-)-tonkinenin A; (-)-qvarigranol G; キラル-4-オキシシクロヘキセノン; 触媒; 不斉配位子; 光学分割; シリルエーテル; (+)-pipoxide; (-)-epizeylenol

The asymmetric olefin migration reaction catalyzed by cationic Rh-complex ligated with chiral BINAP had been successfully carried out for the meso type enediol silyl ether having bicyclo [2.2.1] ring system in its background and 7-membered ring system as substrates. However, applications of this reaction to the other simplified meso substrates (e.g.8-membered ring substrate or 6-membered ring substrates) did not gave satisfactory results. Therefore, the requirement to afford high selectivity of this asymmetric olefin migration reaction was suggested that at least some bulky ether subtituents are necessary at the both allylic positions.On the other hand, keto-silyl ether having high optical purity obtained by this methodology was applied to natural products syntheses. As a result, (-)-malyngolide, (-)-shikimic acid, (-)-quinic acid, (-)-zeylenol, (+)-pipoxide, (-)-uvarigranol G, (-)-isoretronecanl, (+)-trachelanthamidine, and two kinds of cyclohexenone derivatives could be synthesized as the optically active form. Furthermore, the proposed structure of (-)-tonkinenin A could be revised and (-)-epizeylenol could be disproved.

以双环[2.2.1]环为背景，七元环为底物，手性BINAP配体阳离子铑配合物催化的不对称烯烃迁移反应已成功地进行。然而，将该反应应用于其他简化的内消旋底物（例如8元环底物或6元环底物）并没有得到令人满意的结果。因此，为保证不对称烯烃迁移反应的高选择性，在两个烯丙基位置上至少要有一些大的醚取代基.另一方面，通过该方法得到的高光学纯度的酮基硅醚被应用于天然产物的合成.结果表明，（-）-马林高内酯、（-）-莽草酸、（-）-奎尼酸、（-）-zeylenol、（+）-pipoxide、（-）-uvarigranol G、（-）-isoretronecanl、（+）-络石脒和两种环己烯酮衍生物均为光学活性形式。此外，（-）-东京宁A的拟议结构可以被修改，并且（-）-表苯酚可以被反驳。

项目成果

Kou Hiroya: "Preparation of the Synthetic Equivalents of Chiral Cyclohexadienone and Cycloheptadienone : The Enantio-and Diastereo-controlled Synthesis of(-)-Clavularin B"Synlett. 529-532 (1999)

Kou Hiroya：“手性环己二烯酮和环庚二烯酮的合成等价物的制备：(-)-Clavularin B 的对映体和非对映体控制合成”Synlett。

Kou Hiroya: "Preparation of the Synthetic Equivalnets of Chiral Cyclohexadienone and Cycloheptadienone : The Enantio and Diastereo-controlled Synthesis of (-)-Clavularin B" SYNLETT. 印刷中. (1999)

Kou Hiroya：“手性环己二烯酮和环庚二烯酮的合成等价物的制备：(-)-Clavularin B 的对映体和非对映体控制合成”SYNLETT 已出版。

Hiroyuki Konno: "An Enantio-and Diastereoselective Synthesis of (-)-Isoretronecanol and (+)-Trachelanthamidine from a Meso Precursor."Heterocycles. 49・1. 33-37 (1998)

Hiroyuki Konno：“从内消旋前体中合成 (-)-异丙醇和 (+)-Trachelanthamidine”。杂环 49・1 (1998)。

Kou Hiroya: "The First Enantiocontrolled Synthesis of Naturally Occurring Polyoxygenated Cyclohexenylmethanol Dibenzoates, (-)-Zeylenol, (-)-Uvarigranol G, (-)-Tonkinenin A and (+)-Pipoxide."Chemical Communications. 21. 2197-2198 (1999)

Kou Hiroya：“首次对映控制合成天然存在的多氧化环己烯基甲醇二苯甲酸酯、(-)-Zeylenol、(-)-Uvarigraanol G、(-)-Tonkinenin A 和 ( )-Pipoxy。”化学通讯。

Kou Hiroya: "Preparation of the Synthetic Equivalents of Chiral Cyclohexadienone and Cycloheptadienone :The Enantio- and Diastereo-controlled Synthesis of (-)-Clavularin B"Synlett. 5. 529-532 (1999)

Kou Hiroya：“手性环己二烯酮和环庚二烯酮的合成等价物的制备：(-)-Clavularin B 的对映体和非对映体控制合成”Synlett。