Synthesis and Asymmetric Recognition of Chiral Calixarenes

手性杯芳烃的合成与不对称识别

• 批准号: 02453094
• 负责人: SHINKAI Seiji
• 金额: $ 3.2万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453094/
• 关键词: Calixarenes; Optical activity; Asymmetric recognition; Host・guest chemistry; Inclusion compounds; Molecular recognition; Macrocycles; Ion selectivity; 包接化合物; 不斉識別; ホスト化合物; トポロジ-異性; シクロファン; 光学分割

Calixarenes act as novel host molecules not only for metal ions but also for charged and uncharged organic molecules. The purpose of the present research was to design such calixarenes that can asymmetrically recognized optically-active organic molecules. The research strategies are (1) introduction of optically-active substituents and (ii) asymmetric arrangement of substituents on the calixarene ring. Chiral calixarenes synthesized on the basis of strategy (1) showed the selective binding toward chiral guest molecules, which was easily detected by circular dichroism.Strategy (2) involves a new idea in which more than three different substituents are arranged in (R) direction or (S) direction. however, if ring inversion takes place, these optical isomers can racemize. we thus developed a new synthetic method by which inversion of the calix[4]arene ring could he suppressed. We finally succeeded in optical resolution by using a chiral-packing HPLC column. This is the first example for optical resolution of ring-originating, chiral calix[4]arenes.Several attempts to use these chiral calixarenes for asymmetric molecular recognition were reported.

钙棒烯可作为金属离子的新型宿主分子，而且是带电和未充电的有机分子的新宿主分子。本研究的目的是设计可以不对称识别的光学活性有机分子的这种钙棒烯。研究策略是（1）引入光学活性取代基和（ii）在钙甲环上取代基的不对称排列。基于策略（1）合成的手性钙棒素表现出了与手性宾客分子的选择性结合，该分子很容易通过圆形二分离症检测到，斯特拉提症（2）涉及一个新的想法，其中三种以上不同的取代基在（R）或（S）方向上排列了三种以上的取代基。但是，如果发生环反转，这些光学异构体可能会发生种族化。因此，我们开发了一种新的合成方法，通过这种方法可以抑制Calix [4] Arene环的反转。我们最终通过使用手动包装HPLC列成功地完成了光学分辨率。这是据报道，使用这些手性钙钙甲烯烯作为非对称分子识别的几个尝试，这是响环的光学分辨率[4]领域的第一个示例。

项目成果

S. Shinkai, T. Arimura, H. Kawabata, H. Murakami, K. Araki, K, Iwamoto, T. Matsuda: "Synthesis and Optical Resolution of an Asymmetrically Substituted Calix[4]arene" J. Chem. Soc., Chem. Commun.1734-1736 (1990)

S. Shinkai、T. Arimura、H. Kawabata、H. Murakami、K. Araki、K、Iwamoto、T. Matsuda：“不对称取代的杯[4]芳烃的合成和光学拆分”J. Chem。

T. Arimura, S. Shinkai: "Formation of Molecular Complexes with Calixarenes as Detected by Induced Circular Dichroism" Bull. Chem. Soc. Jpn.64. 1896-1900 (1991)

T. Arimura、S. Shinkai：“通过诱导圆二色性检测到杯芳烃分子复合物的形成”公牛。

T.Nagaski: "Synthesis and Solvent Extraction Properties of a Novel CalixareneーBased Uranophile Bearing Hydroxamate Groups" J.Chem.Soc.,Perkin Trans.1. 2617-2818 (1990)

T. Nagaski：“新型杯芳烃基含异羟肟酸基团的亲铀试剂的合成和溶剂萃取特性”J.Chem.Soc.，Perkin Trans.1 (1990)。

K. Iwamoto, A. Yanagi, K. Araki, S. Shinkai: "Syntheses of Isomers from p-t-Butylcalix[4]arne. Strategies for Regioselective Alkylation on the Lower Rim" Chem. Lett.1991. 473-476 (1991)

K. Iwamoto、A. Yanagi、K. Araki、S. Shinkai：“从 p-t-Butylcalix[4]arne 合成异构体。下环区域选择性烷基化策略” Chem。

S.Shinkai: "Bioorganic Chemistry Frontiers" Springer Verlag, 34 (1990)

S.Shinkai：“生物有机化学前沿”Springer Verlag，34（1990）