| Project/Area Number |
11305064
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
有機工業化学
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
YOSHIDA Jun-ichi Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (30127170)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥42,980,000 (Direct Cost: ¥41,900,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2001: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2000: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 1999: ¥34,700,000 (Direct Cost: ¥34,700,000)
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| Keywords | oxidation potential / electro-auxiliary / orbital interaction / organometallic reaction / アルコキシカルベニウムイオン / 分子設計 / 分子変換 / 電子移動 / 炭素-炭素結合形成 / 分子内配位 |
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| Research Abstract |
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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