Tetrahedrane and Cyclobutadiene: Synthesis and Structure of Highly Strained Hydrocarbons

四面体和环丁二烯：高应变烃的合成和结构

• 批准号: 23550042
• 负责人: NAKAMOTO Masaaki
• 金额: $ 3.33万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011 至 2013
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23550042/
• 关键词: 高歪み化合物; ケイ素化合物; テトラヘドラン; シクロブタジエン; シグマーパイ共役; 光誘起異性化; 高歪みシグマ結合; シグマ－パイ共役; 反芳香族性; Diels-Alder反応; ケイ素置換基; 高歪み分子; 原子価異性化; ケイ素; 高歪みσ結合; σ-π共役; へテロ原子

Tetrahedrane is a hydrocarbon with highly strained C-C sigma bonds. Because of the extremely strained skeleton, the increase in the energy level of C-C sigma-bond orbitals results in the sigma-pi conjugation. Cyclobutadiene is one of valence isomers of tetrahedrane and a cyclic unsaturated compound with four pi-electrons within a rectangular planar four-membered ring.We have investigated the synthesis, structural analysis and properties of substituted tetrahedranes stabilized by silyl groups. The perfluoroaryl substituted cyclobutadiene derivatives were prepared as air- and moisture-sensitive red solids by the photochemical isomerization of the corresponding tetrahedranes. The first aryl substituted cyclobutadienes were characterized by spectroscopic data as well as by Xray crystallography. We also developed new versatile synthetic routes of substituted tetrahedranes, and reported more than 20 stable derivatives up to now.

四面体是具有高应变的C-C Sigma键的烃。由于骨骼极为紧张，C-C Sigma键入轨道的能级增加导致Sigma-Pi结合。环丁烯是四面体的价异构体之一，是在矩形平面四元环内具有四个Pi-Electron的环状不饱和化合物。我们研究了由Silyl组稳定的四面体的合成，结构分析和特性。通过相应的四面体的光化学异构化制备了全氟酰胺替代的环丁二烯衍生物作为空气和水分敏感的红色固体制备。第一个芳基取代的环丁烷的特征是光谱数据以及X射线晶体学的特征。我们还开发了替代四面体的新的多功能合成途径，并报告了20多个稳定的衍生物。

项目成果

Photoisomerization of Perfluoroaryltetrahedranes to Perfluoroarylcyclobutadienes

• DOI: 10.1021/ja208354x
• 发表时间: 2011-10-19
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Inagaki, Yusuke;Nakamoto, Masaaki;Sekiguchi, Akira
• 通讯作者: Sekiguchi, Akira

高周期典型元素化合物の電気化学的特性と電池への応用

高周期族元素化合物的电化学性能及其在电池中的应用

• 发表时间: 2013
• 作者: 丸山仁;中野秀之;中本真晃;関口 章
• 通讯作者: 関口 章

Functionalized Tetrahedranes; Structures, Electronic Properties and Reactivities

功能化四面体；

• 发表时间: 2012
• 作者: Y. Kobayashi;M. Nakamoto;A. Sekiguchi
• 通讯作者: A. Sekiguchi

Structure and Reactivity of Silylsubstituted Tetrahedranes and Cyclobutadienes

甲硅烷基取代的四面体和环丁二烯的结构和反应性

• 发表时间: 2012
• 作者: Y. Inagaki;M. Nakamoto;A. Sekiguchi
• 通讯作者: A. Sekiguchi

Synthesis and Reactions of Stable Tetrahedranes, and Its Valence Isomerization to Cyclobutadiene Derivatives

稳定四面体的合成、反应及其化合价异构化生成环丁二烯衍生物

• 发表时间: 2012
• 作者: M. Nakamoto;Y. Inagaki;T. Ochiai;Y. Kobayashi;A. Sekiguchi
• 通讯作者: A. Sekiguchi