Synthesis and catalytic reactivity of orgamometaeeics possessing cavity
空腔有机修饰化合物的合成及催化反应活性
基本信息
- 批准号:10650848
- 负责人:
- 金额:$ 2.24万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (C)
- 财政年份:1998
- 资助国家:日本
- 起止时间:1998 至 1999
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
This research has been focused on to develop new synthetic catalysts, which would mimic the high reactivity and selectivity in enzymatic reactions. The catalysts have been so designed to have a metal-center as an active site and a cavity as a recognition site, that they would catalyze cationic carbon-carbon formation reactions, such as polyene cyclization reactions and glycosylation reactions. We have also investigated a new synthetic methodology for the effective synthesis of the cavity molecules. We find followings.1. New metal ligands, which possess optically active binaphtol moiety as a metal chelating site and dendritic branch moiety as a recognition site, have been successfully synthesized. Complexation of the ligand with Lewis acidic metals gives corresponding optically active metal catalysts, which catalyze asymmetric carbon-carbon bond formation reactions.2. A new glycosylation reaction has been developed. The telluroglycosids are activated under mild oxidative conditions, and give α-and β-anomers selectively depending on the reaction conditions.3. Development of new synthetic methodologies for the synthesis of cavity molecules has been examined by using radical reaction. Telluroglycosides undergo stereochemical isomerization under photochemical and thermal conditions. The isomerization involves reversible generation of glycosyl radicals which are formed by the hemolytic C-Te bond cleavage.4. The radicals described above react with alkynes and isonitriles to give the corresponding group-transfer products. The C-Te bond of the product also undergoes the reversible hemolytic cleavage and the recombination of the resulting radicals.
因此,开发新型的合成催化剂,模拟酶催化反应的高反应活性和高选择性,是近年来的研究热点。催化剂已经被设计成具有作为活性位点的金属中心和作为识别位点的空腔,使得它们将催化阳离子碳-碳形成反应,例如多烯环化反应和糖基化反应。我们还研究了一种新的合成方法,有效地合成腔分子。我们发现如下。1.合成了具有光学活性的联萘酚结构和树枝状分支结构的金属配体。配体与刘易斯酸性金属络合得到相应的光学活性金属催化剂,催化不对称碳-碳键形成反应.发展了一种新的糖基化反应。碲苷在温和的氧化条件下被活化,并根据反应条件选择性地生成α-和β-端基异构体.利用自由基反应研究了空穴分子合成新方法的发展。碲苷在光化学和热条件下发生立体化学异构化。异构化涉及通过溶血性C-Te键断裂形成的糖基自由基的可逆产生。上述自由基与炔和异腈反应,得到相应的基团转移产物。产物的C-Te键也经历可逆的溶血裂解和所产生的自由基的重组。
项目成果
期刊论文数量(19)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
S.Yamago: "Thermal Hetero[3+2]Cycloaddition of Dipolar Trimethylenemethane to N-Sulfonyl and N-Acyl Imines"Chemistry Letters. 879-880 (1999)
S.Yamago:“偶极三亚甲基甲烷与 N-磺酰基和 N-酰基亚胺的热杂[3 2]环加成”化学快报。
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S.Yamago: "Synthesis of Vinylic C-Glycosides from Telluroglycosides. Addition of Photochemically and Thermally Generated Glycosyl Radicals to Alkynes"Terahedron Letters. 40. 2343-2346 (1999)
S.Yamago:“从碲糖苷合成乙烯基C-糖苷。光化学和热生成的糖基自由基与炔烃的加成”四面体字母。
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S.Yamago: "Reverside Generation of Glycosyl Radicals from Telluroglycosides under Photochemical and Thermal Conditions"Tetrahedron Letters. 40. 2339-2342 (1999)
S.Yamago:“在光化学和热条件下从碲糖苷生成糖基自由基”四面体快报。
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- 影响因子:0
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S.Yamago: "Radical Mediated Imidoylation of Telluroglycosides, Insertion of Isonitrites into Glycosidic Carbon-Tellurium Bond"Terahedron Letters. 40. 2347-2350 (1999)
S.Yamago:“碲糖苷的自由基介导的亚胺酰化,将异亚硝酸盐插入糖苷碳碲键”四面体字母。
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- 影响因子:0
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S.Yamago: "Synthesis of Optically Active Dendritic Binaphthds and Their Metal Complexes for Asymmetric Catalysis"Tetrahedron Letters. 39. 3787-3786 (1998)
S.Yamago:“用于不对称催化的光学活性树枝状联萘及其金属配合物的合成”四面体快报。
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YAMAGO Shigeru其他文献
YAMAGO Shigeru的其他文献
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{{ truncateString('YAMAGO Shigeru', 18)}}的其他基金
Development of Stereospecific Cationic Polymerizationthrough Intramolecular Participation at Polymer-end
通过聚合物末端分子内参与的立体定向阳离子聚合的发展
- 批准号:
23655039 - 财政年份:2011
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Challenging Exploratory Research
Precise control of radical reaction utilizing the synergistic effects of heavier heteroatom compounds
利用较重杂原子化合物的协同效应精确控制自由基反应
- 批准号:
18064015 - 财政年份:2006
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
Development of Novel Radical Chemistry Utilizing the Heavy Group 15 Heteroatom Compounds
利用重15族杂原子化合物开发新型自由基化学
- 批准号:
17205013 - 财政年份:2005
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (A)
Development of New Radical Coupling Reactions at Carbon-Heteroatom Multiple Bonds
碳-杂原子多重键上新型自由基偶联反应的发展
- 批准号:
14340229 - 财政年份:2002
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
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