Geminal Bond Participation at the Transition States
| Project/Area Number |
10640576
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | Gifu University |
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Principal Investigator |
INAGAKI Satoshi Faculty of Engineering, Gifu University, Professor, 工学部, 教授 (10108061)
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| Co-Investigator(Kenkyū-buntansha) |
NARUSE Yuji Faculty of Engineering, Gifu University, Assistant Professor, 工学部, 助手 (10192684)
ISHIDA Masaru Faculty of Engineering, Gifu University, Associate Professor, 工学部, 助教授 (30135181)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1999: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1998: ¥1,600,000 (Direct Cost: ¥1,600,000)
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| Keywords | reactivity / selectivity / transition state / geminal bond participation / Diels-Alder Reaction / Cope rearrangement / Diagonalization Reaction / ジェミナル結合 / ディールス-アンダー反応 |
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| Research Abstract |
We analyzed the interactions of bonds at the trasition states of the Diels-Alder reaction between butadiene and ethylene, the Cope rearrangement of 1,5-hexadiene, and the electrocyclic reaction of 1,3-cyclohexadiiene. The electron delocalization from two σ bonds between a reacting center and substituents was found to have the bonding-antibonding properties opposite to each other. The delocalization from the geminal bonds at the Z-positions is bonding to the πbonds of the dienophile in Diels-Alder reaction and to the other reacting π bonds in the Cope rearrangement and the electrocyclic reaction. Electron donating bonds at the Z-positions were then predicted to enhance the reactivities of the dienes in the Diels-Alder reactions and the Cope rearrangements than those at the E-positions. Electropsitive substituents was predicted to prefer the inward rotation in the electrocyclic reactions. These predictions have been confirmed by ab initio molecular orbital and density functional theory calculations of the activation energies of the reactions.
In summary, the geminal bond participation is significant in organic reactions, and electron donating bonds prefer the positions inside the cyclic structures of the trasition states.
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Report
(3 results)
Research Products
(8 results)
