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.

我们分析了键在丁二烯和乙烯之间的Diels-Alder反应的过渡状态下的键相互作用，1,5-己二烯的COPE重排以及1,3-循环的电循环反应。发现来自反应中心和替代物之间的两个σ键的电子离域化具有彼此相反的键合 - 抗抗原特性。从Z位的Geminal键的定位是在Diels-Alder反应中与Dinophile的πBOND键合，并与COPE重排和电磁反应中的其他反应π键结合在一起。然后，预测在Z位的电子捐赠键比E位置上的Diels-Alder反应和COPE重排的二烯的反应性增强。预测电向替代物更喜欢电循环反应中的内向旋转。这些预测已通过从头算分子轨道和密度函数理论的计算来证实，对反应的激活能计算。总而言之，Geminal键参与在有机反应中很重要，并且电子捐赠键更喜欢过渡状态的环状结构内的位置。

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）。