Development and Application of Orbital theory for Steric Control and Design

空间控制与设计轨道理论的发展与应用

基本信息

批准号：
63550620
负责人：
INAGAKI Satoshi
金额：
$ 1.02万
依托单位：
Gifu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

1. We developed and applied a theoretical model and a method for analyzing the mechanism of delocalization of delta-electrons between bonds. The following conclusions are drawn. (1) The preference of antiperiplanar arrangement of vicinal donor-acceptor bonds can be attributed to the seminal delocalization from the intervening bond to the acceptor bond as well as vicinal delocalization between the donor and acceptor bonds. (2) The delocalization between the geminal delta-bonds is antibonding and decreases as the bond angle narrows. The stability of cyclopropane unexpected from its small bond angle cannot be explained by delta-aromaticity but the small extent of the antibonding geminal delocalization. (3) delta-Electrons of Si-Si bonds delocalize well. (4) The P-P bonds have high p-character.2. Selectivities of deprotonation of dimethyl derivatives of aromatic compounds suggested that through-bond interaction could be controlled by inductive effects, and that the carbaniodic centers should interact with the aromatic rings more strongly than expected. 3. Ab initio MO calculations showed a possibility of a new elementary process, i.e., zigzag collapse of 4-membered halonium ions, and the origin of syn-addition of F_2 to olefins.4. A new aspect of substituent effects, conformational adaptation, was proposed.5 pi-facial selectivities of Diels- Alder reactions of 5-substituted cyclopentadiene are controlled by the orbital energy of the substituent, which exhibits effects on the properties of the frontier orbitals at the reaction sites.6. The first method for abstracting a proton from the pi-excessive heteroaromatic molecules were developed and applied to regiospecific functionalization of the methyl group of 2-methyindole.7. Relative stabilities of condensed 5-membered ring heteroaromatic isomers are determined by [6e/6p] rather than [6e/4p] and [6e/5p] conjugations.

1。我们开发并应用了一个理论模型和一种分析键之间三角洲电源定位机理的方法。得出以下结论。（1）替代供体受感受器键的抗乳头排列可以归因于从中间键到受体键以及供体键和受体键之间的替代链接的开创性）。（2）Geminal Delta键之间的离域是抗反键的，并且随着键角变窄而减小。环丙烷从其小键角出现意外的稳定性不能用三角芳族性来解释，而是抗抗demonding Geminal Delocalization的范围很小。（3）SI-SI键的三角电子链接良好。（4）P-P键具有高p-character.2。芳族化合物二甲基衍生物的去质子化的选择性表明，贯穿键的相互作用可以通过电感效应来控制，并且carbaniodic中心应与芳族环相互作用，比预期的更强烈。 3。从头算机计算显示了新的基本过程，即4成元的卤素离子的锯齿形崩溃，以及F_2与烯烃合成的起源。4。提出了取代效应的一个新方面，即构象适应性。5多质子反应的5种阳离子反应的pi-种族选择性由取代基的轨道能量控制，这表现出对边界轨道在边界轨道特性的影响反应位点6。开发了从pi excessive杂虫分子中抽象质子的第一种方法，并应用于2-甲基二烷基甲基的雷神官能化功能。7。冷凝的5元环异构体的相对稳定性由[6E/6P]而不是[6E/4P]和[6E/5P]共轭确定。