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，结构和功能观点引起了广泛的兴趣。在目前的DY中，我们报告了基于ACHIRAL聚螺旋形成（（4-二羟基二苯甲酰基）乙炔）（聚-1）（聚-1）和聚（4-二异丙基胺甲基苯基苯基苯基）乙酰乙基（Poly-2）的螺旋形成，并通过光学上的活性分子，例如Chiriins，Chiriins，Chiriins，例如（4-羟基甲基甲基苯基苯基）。 分别。棉花效应的裂开型和大小可以用作确定胺，糖或酸的手性的新型探针。poly-1和poly-2通过与[RH（NBD）CL] 2的立体特异性聚合一起制备。它们在静脉内构成了uv comperiation hyremations comperried hyremations prolimations the Proliment the Proliment the Proliment the Proliment the the Prolimin the Prodimine the Prodimine the Idemin the Prodimine the Idemin the Idemin the the the the the the the ICD。例如，Poly-1显示了具有各种手性分子的ICD，例如二醇，氨基醇，羟基羧酸，二羧酸，二氨基二氨基酸，二二氨基蛋白...更多的ES，碳水化合物，碳碳水化合物和立体溶液，取决于构型和立体化学溶液的水溶液。 Poly-2在与光学活性羧基和α-羟基酸络合时也显示出类似的ICDS。我们还发现了由手性多苯基乙二醇（Poly-3）轴承手性氨基醇残基的新型螺旋 - 螺旋转变，这些旋转氨基醇残基是由与脊椎酸盐诱导的。 poly-3是一种光学活性聚合物，在紫外可见区域显示ICD。然而，手性酸的结合，例如（R） - 丙酸和（R）-1-苯基丙酸与Poly-3的结合，导致溶液中Poly-3的ICD急剧变化，原因是X-螺旋过渡的溶液中的ICD变化，而Poly-3的CD光谱在Poly-3的CD频谱中也很难变化。因此，多-3的ICD的变化可以用作手性识别酸的探针。尽管在多肽，多核苷酸和聚合物中已经观察到了这种构象转变，但它们的螺旋 - 透感受外部运动因子的控制，包括pH，温度，光和盐浓度。这可能是外部手性因子通过非对映组酸基碱相互作用引起的螺旋螺旋旋转过渡的第一个例子。Poly-3用作非对称酒精的光学活性催化剂。在存在催化量的聚-3的情况下，通过苯甲醛与二乙基的反应获得的对映体过量的1-苯基乙醇为30-49％。较少的

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。