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]环加成反应的新进展为了探索使用具有乙炔二钴络合物部分和烯醇硅醚部分的五碳单元的[5+2]环加成反应的范围和局限性，考察了与各种富电子烯烃以及芳香族化合物的反应。虽然芳香族化合物，包括苯甲醚和苯胺衍生物没有得到好的结果，与一个亚联二烯衍生物的反应被发现得到所需的七元环加成物在良好的产率。（2）高级环加成反应的发展一个新的六碳单元（传统的五碳单元的同系物）与烯醇三异丙基硅醚进行了平稳的[6+2]环加成反应，得到了具有高立体选择性的八元乙炔二钴配合物。使用烯丙基甲硅烷基醚代替烯醇甲硅烷基醚导致经由[6+3]环加成反应形成九元环。所得环状乙炔二钴配合物通过用CAN处理转化成相应的环壬炔衍生物。另一方面，六碳单元与呋喃的反应通过[6+4]环加成反应得到具有醚桥的十元碳环。（3）在天然产物合成中的应用通过硅氧基丙二烯衍生物的[5+2]环加成反应构建氢化甘菊环骨架的新方法，实现了呋喃醚B的全合成。

项目成果

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）。

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。

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

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.

• DOI: 10.1021/ol034455f
• 发表时间: 2003-04
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: M. Sasaki;K. Tanino;Atsushi Hirai;M. Miyashita

立体特異的鎖状有機分子構築法の開発と天然物合成への展開.

构建立体定向链有机分子的方法的开发及其在天然产物合成中的应用。

• 发表时间: 2004
• 期刊: 化学工業 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
• 通讯作者: 宮下正昭 他