Synthesis and Application of New Compounds with Both Axial and Helical Chiralities

具有轴向和螺旋手性的新化合物的合成及应用

• 批准号: 23350021
• 负责人: INANAGA Junji
• 金额: $ 13.23万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23350021/
• 关键词: 合成有機化学; 分子認識; 構造有機化学; 光学活性オリゴマー; 多機能触媒; 超分子化学; 合成化学; 動的らせんキラリティー; ビナフトールオリゴマー; 酸塩基二元機能触媒; エキシマー

We succeeded in synthesizing 1,1'-bi-2-naphthol (BINOL) oligomers (dimer~octamer), which are directly connected at the 3,3'-positions of (R)-BINOL, in pure states and in good overall yields. The dimer was found to work as an excellent NMR shift reagent for chiral sulfoxides. The corresponding mono-calcium complex and low-valent dinuclear Ti-complex were found to work as a chiral bifunctional catalyst for the Michael reaction of nitromethane and to be effective for the pinacol coupling reaction, respectively, in which induced-fit-type reactions are anticipated. The trimer caused interestingly unique helical assembly of water molecules thus leading to the formation of chiral single strand water wire. It was found that the dynamic chirality of oligoBINOLs could be controlled by external stimuli such as pH. The UV-VIS and CD spectra of oligoBINOLs showed unusual trend on the pentamer indicating the formation of a unispiral structure.

我们成功地合成了1,1'-Bi-2-萘酚（Binol）低聚物（二聚体八聚体），这些低聚物（二聚体）直接在（r）-binol的3,3'位置以纯净状态和良好的总收益率连接。 发现该二聚体可作为手性亚氧化二氧化物的出色NMR移位试剂。发现相应的单钙复合物和低价值双核Ti-复合物可以作为硝基甲烷迈克尔反应的手性双功能催化剂，分别对小甲酸酚偶联反应有效，预计诱导的拟合型反应是预期的。三聚体引起了有趣的独特水分子螺旋组件，从而导致手性单链水线的形成。发现寡素的动态手性可以通过诸如pH等外部刺激来控制。寡素的UV-VIS和CD光谱在五聚体中显示出异常的趋势，表明形成了单偶性结构。

项目成果

不斉識別・不斉制御のための新方法論

不对称识别和不对称控制的新方法

• 发表时间: 2012
• 作者: J-i. Fujita;M. Tachi;K. Murakami;H. Sakurai;Y. Morita;S. Higashibayashi;M. Takeguchi;稲永純二
• 通讯作者: 稲永純二

Asymmetric Catalysis with Reusable Diionic Chiral Rare Earth Metal Complex-Ionic Liquid System

可重复使用的双离子手性稀土金属络合物-离子液体体系的不对称催化

• 发表时间: 2012
• 作者: Bernd M. Schmidt;Berit Topolinski;Mihoko Yamada;Shuhei Higashibayashi;Mitsuhiko Shionoya;Hidehiro Sakurai;Dieter Lentz;Junji Inanaga
• 通讯作者: Junji Inanaga

稲永研究室日本語版、研究内容、新概念の創出、新機能分子の創出

稻长实验室日文版，研究内容，新概念的创造，新功能分子的创造

Functional Organic Molecules : Chiral Discrimination, Controlled Formation of Chirality, Ion Sensing, and Photodynamic Therapy by Two-Photon Absorbing Materials

功能有机分子：手性辨别、手性的受控形成、离子传感和双光子吸收材料的光动力治疗

• 发表时间: 2011
• 作者: W.Nakanishi;S.Hayashi;Y.Katsura;M.Hada;稲永純二;S. Nakazawa ほか;Junji Inanaga
• 通讯作者: Junji Inanaga

Design, Synthesis and Function of Novel Stimuli-Responsive pai-Conjugated Molecules

新型刺激响应型共轭分子的设计、合成及功能

• 发表时间: 2012
• 作者: Satoaki Onitsuka;Akihiko Hatakeyama;Hiroshi Furuno;Junji Inanaga
• 通讯作者: Junji Inanaga