Reaction Design of Medium-sized Ring Structure Based on the Working Hypothesis of Ethereal Oxonium Ylide Formation

基于以太氧叶立德形成工作假说的中型环结构反应设计

基本信息

  • 批准号:
    08455416
  • 负责人:
  • 金额:
    $ 4.93万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
  • 财政年份:
    1996
  • 资助国家:
    日本
  • 起止时间:
    1996 至 1997
  • 项目状态:
    已结题

项目摘要

The ambiphilicity of cerbene-type molecules can be inherited in the form of onium ylides. While ethereal oxonium ylides still continue to elude spectroscopic identification, their formations have been demonstrated indirectly by kinetic measurements, e.g., in the reaction of (biphenyl-4-yl) chlorocarbene with THF.On this basis, we designed novel ring-expansion reactions via bi-and tricyclic oxonium ylides for synthesis.Bicyclooxonium ylides formed in the Rh-catalyzed reaction of diazoketones tethered to five-to eight-membered cyclic ethers, where the tethering chains are one methylene units, underwent a novel three-carbon ring-enlargement reaction to form effectively the corresponding eight-to eleven-membered cyclic ketoethers, respectively. Diazoketones tethered to five-to eight-membered cyclic acetals, where the tethering chains are one or two methylene units, also underwent the similar enlargement reaction. Not only rhodium ketocarbenoids but also free carbenes such as alkylidenecarb … More enes bearing cyclic ethers or acetals behaved similarly to give cyclic dienol ethers. In all the reactions, key intermediates are bicyclooxonium ylides whose reactivity is controlled by the stability of charges and ring-strain.The reaction of bicyclic orthoester bearing a diazocarbonyl function tethered by one methylene unit produced a 9-membered polyoxygenated cyclic ether quantitatively. The enlargement efficiency is not attenuated when the tethering methylene chain is elongated from one to four. This indicates that the formation of tricyclooxonium ylides and their ring-expansion are highly favored by not only the enolate-stabilization but also the presence of three ethereal oxygen atoms in orthoesters which delocalize the positive charge of the ylides to facilitate the formation of ring-enlarged zwitterion (1, n-ambiphile) structure.In addition to the ring-expansion reaction, it was unveiled that oxonium ylides of cyclic ethers show an effective novel ring-opening rearrangement reaction leading to the formation of alkenyloxyketenes known as highly reactive transient species. Less
二苯乙炔型分子的两亲性可以以鎓叶立德的形式遗传。虽然醚氧鎓叶立德仍然继续逃避光谱鉴定,但它们的形成已通过动力学测量间接证明,例如,的反应中在此基础上,我们设计了双环和三环氧鎓叶立德的扩环反应,在铑催化下,重氮酮与五至八元环醚反应生成双环氧鎓叶立德,其中连接链是一个亚甲基单元,进行了一种新的三碳扩环反应,有效地形成相应的八至十一元环酮醚。五元至八元环缩醛系链的重氮酮,其中系链是一个或两个亚甲基单元,也经历了类似的放大反应。不仅有铑酮卡宾,而且还有游离卡宾,如亚烷基卡宾 ...更多信息 带有环醚或缩醛的烯表现类似,得到环状二烯醇醚。在所有反应中,关键中间体是双环氧鎓叶立德,其反应活性受电荷稳定性和环张力的控制,双环原酸酯与重氮羰基的反应定量地生成了9元多氧环醚。当束缚亚甲基链从1延长到4时,放大效率不减弱。这表明三环氧鎓叶立德的形成和扩环不仅受到烯醇化物稳定作用的影响,而且还受到原酸酯中存在的三个醚氧原子的影响,醚氧原子使叶立德的正电荷离域,从而促进扩环两性环的形成(1,n-亲两体)结构。除了扩环反应之外,揭示了环醚的氧叶立德显示出有效的新的开环重排反应,导致形成被称为高反应性瞬时物质的烯氧基烯酮。少

项目成果

期刊论文数量(44)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
A.Oku: "Three-and Four-Carbon Elongation Ring-Expansion Reaction of Cyclic Acetals to Medium-Sized Dioxacycloalkenones." J,Org.Chem.62. 2123-2129 (1997)
A.Oku:“环状缩醛到中等尺寸二氧杂环烯酮的三碳和四碳伸长扩环反应。”
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    0
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T.Harada, S.Ueda, T.M.T.Tuyet, A.Inoue, K.Fujita, M.Takeuchi, N.Ogawa, A.Oku: "General Method for Asymmetric Synthesis of Substituted 2,2'-Biaryldiols via Asymmetric Desymmetrization of 2,2', 6,6'-Tetrahydroxybiphenyl with 1-Menthone" Tetrahedron. 53. 166
T.Harada、S.Ueda、T.M.T.Tuyet、A.Inoue、K.Fujita、M.Takeuchi、N.Okawa、A.Oku:“通过 2 的不对称去对称化不对称合成取代的 2,2-联芳二醇的一般方法
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    0
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T.Harada, T.M.T.Tuyet, K.Hashimoto, M.Hatsuda, A.Oku: "Asymmetric Desymmetrization of 2,2', 6,6'-Tetrahydroxybiphenyl by Using 1,4-Di-O-benzyl-D-threitol as a Chiral Template" Synlett. 1426-1428 (1997)
T.Harada、T.M.T.Tuyet、K.Hashimoto、M.Hatsuda、A.Oku:“使用 1,4-二-O-苄基-D-苏糖醇作为 2,2, 6,6-四羟基联苯的不对称去对称化
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    0
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L.-C.Hu, A.Oku, E.Yamada: "Alkali-Catalyzed Methanolysis of Polycarbonate. A Study on Recycling of Bisphenol A and Dimethyl, Carbonate" Polymer. (in press). (1998)
L.-C.Hu、A.Oku、E.Yamada:“聚碳酸酯的碱催化甲醇分解。双酚 A 和二甲基碳酸酯”聚合物回收利用的研究。
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    0
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A.Oku: "Synthetic Organic Chemistry" in "Comprehensive Applied Chemistry Series" Ed.Y.Ito, No.4.Asakura, Tokyo, 1-57 (1997)
A.Oku:“综合应用化学系列”中的“合成有机化学”Ed.Y.Ito,No.4.Asakura,Tokyo,1-57(1997)
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    0
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OKU Akira其他文献

OKU Akira的其他文献

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{{ truncateString('OKU Akira', 18)}}的其他基金

Study on the Monomer Recycling of Plastic Wastes to Feedstock Chemicals.
塑料废物单体回收制原料化学品的研究。
  • 批准号:
    17560727
  • 财政年份:
    2005
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Multi-Dimensional Interactions in Ensembled Molecular System
集成分子系统中的多维相互作用
  • 批准号:
    09045035
  • 财政年份:
    1997
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Grant-in-Aid for international Scientific Research
Novel Carbon-Carbon Bond Formation Utilizing Selective C-H Bond Insertion by Carbenes.
利用卡宾选择性 C-H 键插入形成新型碳-碳键。
  • 批准号:
    63470080
  • 财政年份:
    1988
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)

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Developement of sequential carbon-carbon bond-forming methods by reactivity control of C1 carbenoid species
通过 C1 类胡萝卜素的反应性控制开发连续碳-碳键形成方法
  • 批准号:
    23K04744
  • 财政年份:
    2023
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    $ 4.93万
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Development of synthetic method for heteroatom-containing polycyclic compounds using carbenoid insertion reaction
类胡萝卜素插入反应合成含杂原子多环化合物的方法开发
  • 批准号:
    20K06946
  • 财政年份:
    2020
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    $ 4.93万
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    Grant-in-Aid for Scientific Research (C)
Safe carbenoid chemistry with sulfoxonium ylides
与亚砜叶立德进行安全的类胡萝卜素化学反应
  • 批准号:
    2263552
  • 财政年份:
    2019
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Studentship
Development of environmentally benign metal carbenoid reactions: For catalysts, asymmetric reactions, natural products synthesis
开发环境友好的金属类胡萝卜素反应:用于催化剂、不对称反应、天然产物合成
  • 批准号:
    16K08158
  • 财政年份:
    2016
  • 资助金额:
    $ 4.93万
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Novel Development of an Amide Insertion Reaction and an Elucidation of metallic Property of Carbenoid Species
酰胺插入反应的新进展和类胡萝卜素金属性质的阐明
  • 批准号:
    16K18840
  • 财政年份:
    2016
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
Development of carbenoid chemistry and synthetic applications
类胡萝卜素化学和合成应用的发展
  • 批准号:
    26860008
  • 财政年份:
    2014
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
SusChEM: Selective C-H Functionalization by Highly Tunable Metalloporphyrin Carbenoid: A Mechanistic Investigation
SusChEM:高度可调金属卟啉类胡萝卜素选择性 C-H 官能化:机理研究
  • 批准号:
    1300912
  • 财政年份:
    2013
  • 资助金额:
    $ 4.93万
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    Continuing Grant
New Directions in Carbenoid Chemistry
类胡萝卜素化学的新方向
  • 批准号:
    1213246
  • 财政年份:
    2012
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Standard Grant
Synthetic chemistry based on Rh(II)-carbenoid reactions and synthesis of alkaloids
基于Rh(II)-类胡萝卜素反应的合成化学和生物碱的合成
  • 批准号:
    37411-2008
  • 财政年份:
    2012
  • 资助金额:
    $ 4.93万
  • 项目类别:
    Discovery Grants Program - Individual
Synthetic chemistry based on Rh(II)-carbenoid reactions and synthesis of alkaloids
基于Rh(II)-类胡萝卜素反应的合成化学和生物碱的合成
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    37411-2008
  • 财政年份:
    2011
  • 资助金额:
    $ 4.93万
  • 项目类别:
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