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首页> 外文学位 >Enantioselective sensing using axially chiral diacridylnaphthalenes.
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Enantioselective sensing using axially chiral diacridylnaphthalenes.

机译：使用轴向手性二ac啶基萘进行对映选择性传感。

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摘要

We have developed the first synthetic route to highly congested, conformationally stable 1,8-diarylnaphthalenes using Pd-catalyzed Stille cross-coupling of 1,8-dibromonaphthalene and acridylstannanes in the presence of CuO. Screening of a wide range of Negishi, Kumada, Suzuki, Hiyama, and Stille cross-coupling procedures for the construction of 1,8-diarylnaphthalenes showed that superior results are obtained through palladium-catalyzed Stille coupling, in particular when undesirable alkyl transfer during transmetalation and dehalogenation can be controlled. 1,8-Diacridylnaphthalenes proved to be stable to syn/anti-isomerization even at high temperatures. Crystallographic and NMR, UV, and fluorescence spectroscopic studies showed that this class of compounds exhibits a rigid structure with two cofacial acridyl rings participating in face-to-face interactions.;The fluorescent diacridylnapthalenes prepared in our laboratory proved very useful for sensing of metal ions and enantiomers of various classes of compounds. We found that syn-1,8-di(4-isopropyl-9-acridyl)naphthalene undergoes highly Fe(III)-selective fluorescence quenching in aqueous solution even in the presence of excess of other metal ions. The fluorescence quenching was also found to be almost independent of counteranion effects.;Enantioselective recognition studies using 1,8-diacridylnapthalene-derived sensors showed stereoselective interactions with a variety of chiral compounds resulting in characteristic fluorescence changes. Fluorescence titration experiments using 1,8-bis(3-(3',5'-dimethylphenyl)-9-acridyl)naphthalene or its N,N'-dioxide revealed enantioselective formation of 1:1 or 1:2 complexes with amino acids and carboxylic acids. The high sensitivity inherent to fluorescence spectroscopy combined with the considerable enantioselectivity and broad application spectrum of this type of chemosensors affords a new tool for real-time analysis of the enantiomeric composition of chiral compounds. Atropisomeric 1,8-bis(3-(3',5'-dimethylphenyl)-9-acridyl)naphthalene N,N'-dioxide was found to effectively coordinate to a variety of metal ions, and the corresponding Sc(III) complex was successfully used for enantioselective recognition of a variety of chiral compounds such as amino acids, amino alcohols, and amines based on UV indicator-displacement assays.;1,8-Dipyridylnaphthalene was used as a template for highly stereoselective solid-state photodimerization of fumaric acid. Crystallization studies with acridine and its 9-halogenated derivatives resulted in the formation of two new polymorphs of acridine and a new dipolar acridone solid-state structure exhibiting second-order optical nonlinearity.
机译：我们已经开发出第一种合成路线，该路线是在CuO存在下，使用Pd催化的1,8-二溴萘和丙烯腈锡烷的Stille交叉偶联来制备高度拥挤，构象稳定的1,8-二芳基萘。筛选了大量用于构建1,8-二芳基萘的Negishi，Kumada，Suzuki，Hiyama和Stille交叉偶联程序，结果表明，通过钯催化的Stille偶联可获得优异的结果，尤其是在重金属化过程中不希望的烷基转移时并且可以控制脱卤。 1,8-二ac啶基萘即使在高温下也对顺/反异构稳定。晶体学和NMR，UV和荧光光谱研究表明，这类化合物显示出具有两个面对面相互作用的二丙烯酰基环的刚性结构。在我们的实验室中制备的荧光双丙烯酰胺基被证明对感测金属离子非常有用。和各种化合物的对映异构体。我们发现，即使在存在其他金属离子过量的情况下，syn-1,8-二（4-异丙基-9-ac啶基）萘在水溶液中也会经历高度Fe（III）-选择性荧光猝灭。还发现荧光猝灭几乎与抗衡阴离子的作用无关。；使用1,8-双丙烯酰胺基传感器的对映选择性识别研究显示与多种手性化合物的立体选择性相互作用，导致特征性的荧光变化。使用1,8-双（3-（3'，5'-二甲基苯基）-9-ac啶基）萘或其N，N'-二氧化物进行的荧光滴定实验表明，与氨基酸的1：1或1：2配合物的对映选择性形成和羧酸。荧光光谱法固有的高灵敏度与此类化学传感器的相当高的对映选择性和广泛的应用范围相结合，为实时分析手性化合物的对映体组成提供了一种新工具。阻转异构的1,8-双（3-（3'，5'-二甲基苯基）-9-ac啶基）萘N，N'-二氧化物可以有效地与多种金属离子和相应的Sc（III）配合物已成功地用于基于紫外线指示剂位移测定的各种手性化合物（如氨基酸，氨基醇和胺）的对映选择性识别。; 1,8-二吡啶基萘用作富马酸高立体选择性固态光二聚化的模板酸。用a啶及其9-卤代衍生物进行的结晶研究导致形成了两个新的of啶多晶型物和一个新的显示出二次光学非线性的偶极a啶酮固态结构。

著录项

  • 作者

    Mei, Xuefeng.;

  • 作者单位

    Georgetown University.;

  • 授予单位 Georgetown University.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2006
  • 页码 225 p.
  • 总页数 225
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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