Geminal Bond Participation at the Transition States

转型国家的双子债券参与

• 批准号: 10640576
• 负责人: INAGAKI Satoshi
• 金额: $ 1.34万
• 依托单位: Gifu University
• 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: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640576/
• 关键词: 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

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.

我们分析了丁二烯与乙烯的Diels-Alder反应、1,5-己二烯的Cope重排和1,3-环己二烯的电环反应的过渡态键的相互作用。反应中心和取代基之间的两个σ键的电子离域具有相反的成键-反键性质。在Diels-Alder反应中，二亲化合物的π键和Cope重排反应及电环反应中的π键在z位上离域。然后预测在z位上的给电子键比在e位上的给电子键更能增强Diels-Alder反应和Cope重排的活性。电取代基在电环反应中倾向于向内旋。这些预测已被从头算分子轨道和密度泛函理论对反应活化能的计算所证实。综上所述，在有机反应中，二元键的参与是很重要的，给电子键倾向于在过渡态的环结构内的位置。

项目成果

Hirotaka Ikeda: "Geminal Bond Participation in the Cope rearrangements of Z- and E-Substituted 1,5-Hexadienes and in the Reverse Reactions"Chem. Lett.. 363-364 (1999)

Hirotaka Ikeda：“Geminal Bond参与Z-和E-取代的1,5-己二烯的Cope重排和逆反应”Chem。

Hirotaka Ikeda: "Definition and Design of Diagonalization Reactions. Reactions of 1,2-Heteraazetidine N-Oxides"Terahedron. Lett.. 40. 8893-8896 (1999)

Hirotaka Ikeda：“对角化反应的定义和设计。1,2-杂氮杂环丁烷 N-氧化物的反应”四面体。

稲垣都士: "Geminal Bond Participation and Reactivities of Z- and E-Substituted Butadienes in the Diels-Alder Reactions"Journal of Organic Chemistry. 63. 7820-7824 (1998)

Toshi Inagaki：“Diels-Alder 反应中 Z- 和 E-取代的丁二烯的偕键参与和反应性”有机化学杂志 63. 7820-7824 (1998)。

池田博隆: "Definition and Design of Diagonalization Reactions. Reactions of 1,2-Heteradzetidin N-Oxides"Tetrahedron Letters. 40. 8893-8896 (1999)

Hirotaka Ikeda：“对角化反应的定义和设计。1,2-Heteradzetidin N-氧化物的反应”Tetrahedron Letters 40。8893-8896 (1999)

稲垣都士: "Geminal Bond Porticipation and Reactivities of Z-VS E-Sukotituted Butadienes in the Diels-Alder Reactions" the Journal of Organic Chemistry. 63・22. 7820-7824 (1998)

Toshi Inagaki：“Diels-Alder 反应中 Z-VS E-Sukotituated 丁二烯的孪晶键参与和反应性”有机化学杂志 63・22（1998）。