Conformational Panorama and Chirality Controlled Structure-Energy Relationship in a Chiral Carboxylic Acid Dimer.,Angewandte Chemie International Edition

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Conformational Panorama and Chirality Controlled Structure-Energy Relationship in a Chiral Carboxylic Acid Dimer.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-06-04 , DOI: 10.1002/anie.202005685
Fan Xie ₁ , Nathan A Seifert _{1,

2} , Wolfgang Jäger ₁ , Yunjie Xu ₁

Affiliation

Chirality recognition in dimers of tetrahydro‐2‐furoic acid (THFA) was studied in a conformer‐specific manner using rotational spectroscopy and theoretical approaches. THFA shows a strong preference for the trans‐ over the cis‐COOH configuration. Two drastically different scenarios are possible for the detectable (THFA)₂: a kinetically preferred dimer bound by feeble interactions between two trans THFAs or a thermodynamically favored dimer with a double hydrogen‐bonded ring structure between two cis subunits. To identify the conformers responsible for the extremely dense rotational spectra observed, it was essential not only to locate several hundred homo/heterochiral (THFA)₂ minima in ab initio calculations but also to evaluate the energetic connectivities among the minima. The study further reveals an interesting chirality dependent structure–energy ordering relationship. A method for enantiomeric excess (ee) determination of THFA is presented using a recently proposed chiral self‐tag approach.

中文翻译：

手性羧酸二聚体的构象全景图和手性控制的结构-能量关系。

使用旋转光谱和理论方法，以特定于构象体的方式研究了四氢-2-糠酸（THFA）二聚体中的手性识别。THFA给出了一个强烈的偏好反式-在独联体-COOH配置。可检测到的（THFA）₂可能存在两种截然不同的情况：通过两个反式THFA之间弱相互作用而结合的动力学上优选的二聚体，或在两个顺式亚基之间具有双氢键合环结构的热力学上有利的二聚体。为了鉴定导致观察到的极其稠密的旋转光谱的构象异构体，不仅要定位数百个同型/杂环基（THFA）₂从头算的最小值，也可以评估最小值之间的能量连通性。该研究进一步揭示了有趣的手性依赖性结构-能量有序关系。使用最近提出的手性自标记方法，提出了一种测定THFA的对映体过量（ee）的方法。

更新日期：2020-06-04

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