Development of New Methods for Constructing Medium Sized Carbocycles by Using Acetylene Dicobalt Complexes

乙炔二钴配合物构建中型碳环新方法的开发

• 批准号: 14340191
• 负责人: TANINO Keiji
• 金额: $ 6.34万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340191/
• 关键词: Medium Sized Ring; Acetylene Dicobalt Complex; Cycloaddition; Cyclization; Addition Reaction; Carbocation; Enol Eilyl Ether; Allylsilane; 天然物合成; フラン; ルイス酸

(1)New aspects of [5+2] cycloaddition reactionsIn order to explore the scope and limitations of the [5+2] cycloaddition reaction using the five-carbon unit having an acetylene dicobalt complex moiety and an enol silyl ether moiety, the reactions with various electron rich olefins as well as aromatic compounds were examined. Although aromatic compounds including anisols and aniline derivatives gave no good results, the reaction with a siloxyallene derivative was found to give the desired seven-membered cycloadduct in good yield.(2)Development of the higher-order cycloaddition reactionsA new six-carbon unit, a homologue of the conventional five-carbon unit, underwent a smooth [6+2] cycloaddition reaction with an enol triisopropylsilyl ether giving rise to an eight-membered acetylene dicobalt complex with high stereoselectivity. Use of an allyl silyl ether instead of an enol silyl ether resulted in formation of a nine-membered ring via a [6+3] cycloaddition reaction. The resulting cyclic acetylene dicobalt complex was converted into the corresponding cyclononyne derivative by treating with CAN. On the other hand, the reaction of the six-carbon unit and furan afforded a ten-membered carbocycle having an ether bridge through a [6+4] cycloaddition reaction.(3)Application to the synthesis of natural productsTotal synthesis of furanether B was accomplished on the basis of a new method for constructing a hydroazulene skeleton through the [5+2] cycloaddition reaction of a siloxy allene derivative.

（1）[5+2]环加成反应的新方面，以探讨[5+2]环载反应的范围和局限性，使用具有乙炔二氧化甲苯二甲基复合部分和一个enol silyl silyl seltheriotie的五碳单元，以及与各种电子富含电子的olefins and and and and and comptions and and eron and and and and and comptions and and and and artomention and Armotomentic comporations。尽管芳香化合物在内的化合物在内的化合物和苯胺衍生物包括没有良好的效果，但发现与硅氧基因衍生物的反应使所需的七元环载量具有良好的收率。（2）高阶环加成反应的发展，六六碳单位的高阶环反应，与传统的五碳单位的同源性，一cy [6+2] cyc [6+2] cy [6+2] cyc [6+2] cyc [6+2]三异丙基甲硅烷基乙醚产生具有高立体选择性的八元乙炔双甲苯。使用烯丙基甲硅烷基醚而不是烯醇甲硅烷基醚，从而通过A [6+3]环加成反应形成了9元环。通过用CAN处理，将所得的环状乙炔双核络合物转化为相应的cyclononyne衍生物。另一方面，六碳单元和呋喃的反应提供了一个十碳环旋转菌，该碳纤维通过[6+4]的环载反应反应。（3）将天然产物体面合成的合成用于furanether B的合成，基于构建Hydroazulene s s seliv a s cyc cy 5+2] Cy 5+2]基于新方法的基础。

项目成果

Ryoichi Nakamura: "Total Synthesis of Scytophycin C (Part 2) : The Coupling Reaction of the C(1)-C(18) Segment (Segment A) and the C(19)-C(31) Segment (Segment B), a Key Macrolactonization, and the Crucial Terminal Amidation Reaction"Organic Letters. 5・20

Ryoichi Nakamura：“Scytophycin C 的全合成（第 2 部分）：C(1)-C(18) 片段（片段 A）和 C(19)-C(31) 片段（片段 B）的偶联反应， a 关键的大环内酯化和关键的末端酰胺化反应”有机信件。5・20

Ryoichi Nakamura: "Total Synthesis of Scytophycin C (Part 1) : Stereoselective Syntheses of the C(1)-C(18) Segment (Segment A) and the C(19)-C(31) Segment (Segment B)"Organic Letters. 5・20. 3579-3582 (2003)

Ryoichi Nakamura：“Scytophycin C 的全合成（第 1 部分）：C(1)-C(18) 片段（片段 A）和 C(19)-C(31) 片段（片段 B）的立体选择性合成”有机信件5・20。

Minoru Sasaki: "The C2 Selective Nucleophilic Substitution Reactions of 2,3-Epoxy Alcohols Mediated by Trialkyl Borates : The First Endo-Mode Epoxide-Opening Reaction through an Intramolecular Metal Chelate"Organic Letters. 5・10. 1789-1791 (2003)

佐佐木稔：“三烷基硼酸盐介导的 2,3-环氧醇的 C2 选择性亲核取代反应：通过分子内金属螯合物的首次内型环氧化物打开反应”有机快报 5·10（2003 年）。

Natural Product Synthesis Based on New Acyclic Stereocontrol. Stereoselective Total Synthesis of Zincophorin, the lonophore Antibiotic, and Scytophycin C, an Antitumor Marine Macrolide.

基于新型非环立体控制的天然产物合成。

• 发表时间: 2004
• 期刊: J.Synth.Org.Chem., Japan 62
• 作者: K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;Y.Iwata et al.;T.Horiuchi;K.Tanino et al.;N.Iki;T.Kajiwara;T.Horiuchi;Y.Iwata et al.;N.Iki;M.Miyashita et al.;T.Kajiwara;R.Nakamura et al.;T.Horiuchi;I.Kuwajima et al.;T.Kajiwara;宮下正昭;N.Kon;Y.Iwata et al.;F.Hamada;T.Kajiwara;K.Tanino et al.;Y.Iwata et al.;T.Kajiwara;M.Miyashita et al.;N.Morohashi;R.Nakamura et al.;T.Kajiwara;I.Kuwajima et al.;N.Kon;F.Hamada;M.Miyashita;T.Kajiwara;Y.Iwata et al.;K.Tanino et al.;T.Kajiwara;N.Morohashi;Y.Iwata et al.;T.Kajiwara;M.Miyashita et al.;N.Kon;R.Nakamura et al.;F.Hamada;M.Sasaki et al.;T.Kajiwara;Xiao-Qiang Yu et al.;T.Kajiwara;Y.Kondo;M.Miyashita et al.;T.Takahashi;K.Komatsu et al.;H.Matsumiya;M.Miyashita et al.;Y.Kondo;宮下正昭 他;Xiao-Qiang Yu et al.;T.Takahashi;H.Matsumiya;K.Komatsu et al.;Y.Kondo;M.Miyashita et al.
• 通讯作者: M.Miyashita et al.

Development of New Acyclic Stereocontrol and Its Application to Natural Product Synthesis.

新型无环立体控制的发展及其在天然产物合成中的应用。

• 发表时间: 2004
• 期刊: Chemical Industry 55
• 作者: K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;K.Tanino et al.;Y.Iwata et al.;T.Horiuchi;K.Tanino et al.;N.Iki;T.Kajiwara;T.Horiuchi;Y.Iwata et al.;N.Iki;M.Miyashita et al.;T.Kajiwara;R.Nakamura et al.;T.Horiuchi;I.Kuwajima et al.;T.Kajiwara;宮下正昭;N.Kon;Y.Iwata et al.;F.Hamada;T.Kajiwara;K.Tanino et al.;Y.Iwata et al.;T.Kajiwara;M.Miyashita et al.;N.Morohashi;R.Nakamura et al.;T.Kajiwara;I.Kuwajima et al.;N.Kon;F.Hamada;M.Miyashita;T.Kajiwara;Y.Iwata et al.;K.Tanino et al.;T.Kajiwara;N.Morohashi;Y.Iwata et al.;T.Kajiwara;M.Miyashita et al.;N.Kon;R.Nakamura et al.;F.Hamada;M.Sasaki et al.;T.Kajiwara;Xiao-Qiang Yu et al.;T.Kajiwara;Y.Kondo;M.Miyashita et al.;T.Takahashi;K.Komatsu et al.;H.Matsumiya;M.Miyashita et al.;Y.Kondo;宮下正昭 他;Xiao-Qiang Yu et al.;T.Takahashi;H.Matsumiya;K.Komatsu et al.;Y.Kondo;M.Miyashita et al.;T.Takahashi;H.Matsumiya;M.Miyashita et al.
• 通讯作者: M.Miyashita et al.