Design and Synthesis of Polyacetylenes as a Probe for Chirality of Sugars and Carboxylic Acids

作为糖和羧酸手性探针的聚乙炔的设计与合成

• 批准号: 08651050
• 负责人: YASHIMA Eiji
• 金额: $ 1.41万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08651050/
• 关键词: Polyphenylacetylene; Helix; Induced CD; Helix-Helix Transition; Carboxylic Acid; Chiral Discrimination; Chirality Discrimination; Sugars; ボロン酸; アミン; 誘起らせん

Helical polymers have aroused wide interest from synthetic, structural, and functional viewpoints. In the present dy, we report the induced circular dichroism (ICD) based on the helix formation of achiral poly ((4-dihydroxyborophenyl) acetylene) (poly-1) and poly ((4-disopropylaminomethylphenyl) acetylene) (poly-2) by the complexation with optically active molecules, for instance, chiral amines, sugars, and chiral acids, respectively. The split-type and magnitude of the Cotton effects can be used as a novel probe for determining the chirality of amines, sugars, or acids.Poly-1 and poly-2 were prepared through the stereospecific polymerization with [Rh (nbd) Cl] 2. They exhibited an ICD in the UV-visible region upon complexation with chiral molecules, probably due to the predominantly one-handed helical conformation of the polymers. For instance, poly-1 showed an ICD with various kinds of chiral molecules such as diols, amino alcohols, hydroxycarboxylic acids, dicarboxylic acids, diamin … More es, carbohydrates, and steroids in aqueous solution depending on the configuration and stereochemistry of the molecules. Poly-2 also showed similar ICDs upon complexation with optically active carboxylic and alpha-hydroxy acids.We also found a novel helix-helix transition of optically active polyphenylacetylene (poly-3) bearing chiral aminoalcohol residues induced by the complexation with chiral acids. Poly-3 is an optically active polymer and shows an ICD in the UV-visible region. However, the binding of chiral acids, for instance, (R) -mandelic acid and (R) -1-phenylpropionic acid to poly-3, results in a dramatic change in the ICD of poly-3 in solution owing to a x-helix transition, while the CD spectrum of poly-3 hardly changed even in the presence of excess (S) -mandelic acid and (S) -1-phenylpropionic acid. Therefore, the changes in the ICD of poly-3 can be used as a probe for chiral recognition of the acids. Although such a conformational transition has been observed in polypeptides, polynucleotides, and polymethacrylates, their helix-sense is governed by external achiral factors including pH,temperature, light, and salt concentration. This may the first example of a helix-helix transition induced by external chiral factor through diastereomeric acid-base interactions.Poly-3 was used as an optically active catalyst for asymmetric alkylation. Enantiomeric excess of 1-phenylethanol obtained by the reaction of benzaldehyde with diethylzinc in the presence of catalytic amount of poly-3 was 30 - 49 %. Less

螺旋聚合物从合成、结构和功能的角度引起了人们的广泛兴趣。本文报道了非手性聚（4-二羟基硼苯基）乙炔（poly-1）和聚（4-二异丙基氨基甲基苯基）乙炔（poly-2）分别与手性胺、糖和手性酸络合形成螺旋的诱导圆二色性（ICD）。Cotton效应的分裂类型和大小可以作为一种新的探针来确定胺、糖或酸的手性。它们在与手性分子络合后在UV-可见光区表现出ICD，这可能是由于聚合物的主要单手螺旋构象。例如，聚-1显示出与各种手性分子如二醇、氨基醇、羟基羧酸、二羧酸、二胺、二羟基苯甲酸、二氨基苯 ...更多信息 根据分子的构型和立体化学，在水溶液中可以是糖、碳水化合物和类固醇。Poly-2在与光学活性羧酸和α-羟基酸络合时也表现出类似的ICDs，我们还发现了一种新的带有手性氨基醇残基的光学活性聚苯乙炔（Poly-3）与手性酸络合诱导的螺旋-螺旋转变。Poly-3是一种光学活性聚合物，在UV-可见光区显示出ICD。然而，手性酸，例如（R）-扁桃酸和（R）-1-苯基丙酸与聚-3的结合，由于x-螺旋转变导致聚-3在溶液中的ICD的显著变化，而聚-3的CD光谱即使在过量的（S）-扁桃酸和（S）-1-苯基丙酸存在下也几乎没有变化。因此，聚-3的ICD的变化可以用作酸的手性识别的探针。尽管在多肽、多核苷酸和聚甲基丙烯酸酯中已经观察到这样的构象转变，但是它们的螺旋义由外部非手性因素（包括pH、温度、光和盐浓度）控制。这可能是第一个通过非对映体酸碱相互作用由外手性因素诱导的螺旋-螺旋转变的例子。在催化量的聚-3存在下，苯甲醛与二乙基锌反应得到的1-苯基乙醇的对映体过量为30 - 49%。少

项目成果

E.Yashima: "A Stereoregular Polyphenylacetylene Derivative Bearing an Amino Group as a Probe for Chirality Assignments of Acids by Circular Dichroism" Chem.Lett.1996. 955-956 (1996)

E.Yashima：“带有氨基的立构聚苯乙炔衍生物作为圆二色性酸手性分配的探针”Chem.Lett.1996。

八島栄次: "らせん構造の制御と応用-最近の話題-" 海外高分子研究. 9. 56-59 (1997)

矢岛英二：《螺旋结构的控制与应用——近期课题》海外高分子研究 9. 56-59 (1997)。

E.Yashima: "Poly((4-dihydroxyborophenyl)acetylene) as Novel Probe for Chirality and Structure Assignments of Various Kinds of Molecules Including Carbohydrates and Steroids by Circular Dichroism" J.Am.Chem.Soc.118. 9800-9801 (1996)

E.Yashima：“聚（（4-二羟基硼苯基）乙炔）作为通过圆二色性对包括碳水化合物和类固醇在内的各种分子的手性和结构指定的新型探针”J.Am.Chem.Soc.118。

E.Yashima, T.Matsushima, T.Nimura, and Y,Okamoto: "Enantioseparation on Optically Active Stereoregular Polyphenylacetylene Derivatives as Chiral Stationary Phases for HPLC" Korean Polym.J.4. 139-146 (1996)

E.Yashima、T.Matsushima、T.Nimura 和 Y,Okamoto：“光学活性立构聚苯乙炔衍生物作为 HPLC 手性固定相的对映分离”Korean Polym.J.4。

Y.Okamoto and E.Yashima: Macromolecular Design of Polymeric Materials, K.Hatada, T.Kitayama, and O.Vogl.ed. "Chiral Recognition by Optically Active Polymers". Marcel Dekker, New York, Chap.41, 731-746 (1996)

Y.Okamoto 和 E.Yashima：高分子材料的高分子设计，K.Hatada、T.Kitayama 和 O.Vogl.ed。