New, Rational Synthetic Transformations Based on the Oxidation Potentials as Universal Reactivity Indices
New, Rational Synthetic Transformations Based on the Oxidation Potentials as Universal Reactivity Indices
批准号:
11305064
负责人:
YOSHIDA Jun-ichi
金额:
$27.51万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (A)
财政年份:
1999
资助国家:
日本
项目状态:
已结题
起止时间:
1999 至 2001
中文摘要
我们已经研究了新的合成转换的基础上合理的设计和预测的反应物的反应性,使用的氧化电位作为通用的反应性指数。我们开发了一种新型高效的电动辅助设备; 2-吡啶基甲硅烷基取代的硫醚的氧化电位比未取代的硫醚的氧化电位低得多,而2-吡啶基硅基的作用可以通过吡啶基对硫衍生自由基阳离子的分子内参与来解释,其由起始衬底的单电子氧化产生。2-吡啶基硅基对二价有机硫化合物氧化电位的降低作用强于一般的有机硅基,说明2-吡啶基硅基的碱性强于吡啶基,这是由于吡啶基氮原子的n-轨道与C-Si键的σ-轨道相互作用的结果。因此,2-吡啶基硅基有望在金属催化反应中作为强有力的分子内配体。在内部,我们已经成功地开发了各种有机金属介导的合成反应,包括硅氢加成,Heck型反应,Stille型反应,碳镁化和硅甲基的去质子化。
英文摘要
We have investigated new synthetic transformations based on rational design and prediction of the reactivity of reactants using the oxidation potentials as universal reactivity indices. We have developed a new and highly effective electro-auxiliary ; 2-pyridylsilyl group, which can be also used for removable intramolecular ligand for metal-mediated and catalyzed reactions.The oxidation potential of the α-2-pyridylsilyl-substituted sulfide is considerably lower than that of the non-substituted one, and the effect of 2-pyridylsilyl group can be explained by the intramolecular participation of the pyridyl group to the sulfur-derived radical cation spesies, which are generated by single electron oxidation of the starting substrate. This participation effect is also supported by the fact that 2-pyridylsilyl group possesses stronger effect than ordinary organosilyl group to decrease the oxidation potentials of divalent organosulfur compounds.The results above suggest that the basicity of 2-pyridylsilyl group is stronger than that of pyridine because of the existence of the interaction of the n-orbital of the pyridyl nitrogen and the σ-orbital of the C-Si bond. Therefore, 2-pyridylsilyl group is expected to serve as a powerful intramolecular ligand in metal-mediated and catalyzed reactions. Inside, we have succeeded in developing various organometallic-mediate synthetic reactions, including the hydrosilylation, the Heck-type reaction, the Stille-type reaction, the carbomagnesiation, and the deprotonation of silylmethyl groups.
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Jun-ichi Yoshida: "Regioselective Catalytic Allylic Alkylation Directed by Removable 2-PyMe_2Si Group"Journal of the American Chemical Society. 123. 6957-6958 (2001)
Jun-ichi Yoshida:“Regioselective Catalytic Allylic Alkylation Directed by Removable 2-PyMe_2Si Group”美国化学会杂志。
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Jun-ichi Yoshida: "Facile Generation of [Bis(2-pyridyldimethilsilyl)methyl]lithium and Its Reaction with Carbonyl Compounds. New Method for the Stereoselective Synthesis of Vinylsilanes"Tetrahedron. 57. 5045-5054 (2001)
Jun-ichi Yoshida:“[双(2-吡啶基二甲基甲硅烷基)甲基]锂的简便生成及其与羰基化合物的反应。乙烯基硅烷立体选择性合成的新方法”四面体。
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Jun-ichi Yoshida: ""Organic Quantum Chemistry" H. Fujimoto Ed."Asakurashoten. 181 (2001)
吉田淳一:“《有机量子化学》H. Fujimoto Ed.”朝仓书店。
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Jun-ichi Yoshida: "Pyridyl Group Assisted Deprotonation of a Methyl Group on Silicons Complex Induced Droximity Effect and Novel Hydroxymethylation"The Journal of Organic Chemistry. 66. 3970-3976 (2001)
Jun-ichi Yoshida:“吡啶基辅助甲基在硅络合物上的去质子化诱导的屈肟效应和新型羟甲基化”有机化学杂志。
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共 16 条
Deepening and Developing New Aspects of Flash Chemistry
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批准号:26220804
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项目类别:Grant-in-Aid for Scientific Research (S)
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资助金额:$122.89万
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财政年份:2014
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负责人:YOSHIDA Jun-ichi
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依托单位:
Redox Conversion of Organic Reactive Intermediates
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批准号:20245008
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项目类别:Grant-in-Aid for Scientific Research (A)
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资助金额:$30.78万
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财政年份:2008
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负责人:YOSHIDA Jun-ichi
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依托单位:
Creation and Systematization of New Organic Cation Chemistry
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批准号:17205012
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项目类别:Grant-in-Aid for Scientific Research (A)
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资助金额:$31.95万
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财政年份:2005
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负责人:YOSHIDA Jun-ichi
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依托单位:
Combination of Reactions and Separations for New Organic Synthesis
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批准号:14205125
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项目类别:Grant-in-Aid for Scientific Research (A)
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资助金额:$34.28万
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财政年份:2002
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负责人:YOSHIDA Jun-ichi
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依托单位:
Development of Practical Electron Transfer Driven Reactions for Organic Synthesis
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批准号:11555242
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$8.64万
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财政年份:1999
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负责人:YOSHIDA Jun-ichi
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依托单位:
Organic Synthesis Using Electroauxiliaries
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批准号:07455360
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$4.93万
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财政年份:1995
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负责人:YOSHIDA Jun-ichi
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依托单位:
Umpolung of Organometallic Compounds by Electrochemical Reactions and Its Applications to Carbon-Carbon Bond Formation
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批准号:04640511
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项目类别:Grant-in-Aid for General Scientific Research (C)
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资助金额:$1.28万
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财政年份:1992
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负责人:YOSHIDA Jun-ichi
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依托单位: