Preparation of Tailor-Made Hosts from -Cyclodextrin by Modification of its Cavity

环糊精空腔改性制备定制宿主

• 批准号: 61550585
• 负责人: UENO Akihiko
• 金额: $ 1.28万
• 依托单位: TOHOKU 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: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-61550585/
• 关键词: γ-シクロデキストリン; エキシマー; コンプレックス; スペーサー; アントラセンの光二中量化; ピレン; 包接化合物; 円偏光二色性; アントラセンの光二量化; 立体化学制御; ホスト; ゲスト; アントラセン; 会合; エクシマー; シクロデキストリン; ホスト-ゲスト

-Cyclodextrin ( -CD) can include two molecular species in its cavity. When -CD has an appending arene moiety, the moiety can be expected to act as a spacer, which enables -CD to form 1:1 host-guest complexes by narrowing the large cavity. The purpose of this project is preparing many hosts having voids with desired sizes by using spacer moieties different in bulkiness. From this viewpoint, -CD derivatives having ferrocene, naphthalene, anthracene, and pyrene have been prepared. When the -CD derivatives form complexes with guests, the ferrocene moiety moves outward, whereas the naphthalene moiety enters the cavity. The -CD derivatives hving anthracene and pyrene moieties form association dimers, which convert into 1:1 host-guest complexes on guest addition. The association dimer of pryene-appended -CD exhibits excimer emission, whose intensity diminishes on guest addition. This system was used as a sensory system for detecting a variety of organic compounds. In relation to this project, -CDs having two 9-anthracenecarboxylate moieties at ab, AC, AD, and AE glucose residues were prepared. In these substanecs, two anthracene moieties take different mutual orientations, and the cis-photodimer, that is hardly produced in solution, was produced for AB regioisomer. In the case of photoreaction of -CD derivatives having 1-anthracenecarboxylate moieties, there are four possible photodimers. However, syn-head-head dimer was produced from AB and AC, whereas anti-head-head dimer was produced from AD and AE. These results demonstrate that this " -CD template method" can be used to regulate product stereochemistry in organic reaction.

- 环糊精（-CD）可以在其空腔中包括两种分子物质。当-CD具有附加的芳烃部分时，可以预期该部分充当间隔基，这使得-CD能够通过使大腔变窄而形成1：1的主体-客体复合物。本计画的目的是借由使用不同体积的间隔基来制备具有所需尺寸的孔洞的多个主体。从这个观点出发，已经制备了具有二茂铁、萘、蒽和芘的-CD衍生物。当-CD衍生物与客体形成复合物时，二茂铁部分向外移动，而萘部分进入空腔。具有蒽和芘部分的-CD衍生物形成缔合二聚体，其在客体加成时转化为1：1的主体-客体复合物。缔合二聚体的芘附加的CD表现出激基发射，其强度减弱的客人除了。该系统被用作检测各种有机化合物的传感系统。在这个项目中，-CD具有两个9-蒽羧酸部分在ab，AC，AD和AE葡萄糖残基的制备。在这些物质中，两个蒽基团具有不同的相互取向，AB区域异构体产生了在溶液中几乎不产生的顺式光二聚体。在具有1-anthracenecarboxylate部分的-CD衍生物的光反应的情况下，存在四种可能的光二聚体。然而，顺式头-头二聚体产生于AB和AC，而抗头-头二聚体产生于AD和AE。这些结果表明，这种“-CD模板法”可以用来调控有机反应中产物的立体化学。

项目成果

Fumio Hamada: Bull.Chem.Soc.Jpn.61. 3758-3760 (1988)

滨田文雄：Bull.Chem.Soc.Jpn.61。

Akihiko Ueno: "Strong Binding Ability of Lipophilic Cyclodextrins for Alkali Metal and Alkaline Earth Metal Ions" Chem. Lett.581-584 (1987)

Akihiko Ueno：“亲脂性环糊精对碱金属和碱土金属离子的强结合能力”Chem。

Akihiko Ueno: "Association, Photodimerization, and Induced-fit Types of Host-Guest Complexation of Anthracene-appended -Cyclodextrin Derivatives" J. Am. Chem. Soc.110. 4323-4328 (1988)

Akihiko Ueno：“蒽附加环糊精衍生物的缔合、光二聚化和诱导配合类型的主客体络合”J. Am。

Akihiko Ueno: J.Org.Chem.54. 295-299 (1989)

上野明彦：J.Org.Chem.54。

Akihiko Ueno: J.Am.Chem.Soc.

上野明彦：J.Am.Chem.Soc。