含 BINOL 的手性多孔聚合物作为对映体识别平台,ACS Applied Materials & Interfaces

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含 BINOL 的手性多孔聚合物作为对映体识别平台
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2022-11-23 , DOI: 10.1021/acsami.2c18074
Antonio Valverde-González ₁ , M Carmen Borrallo-Aniceto ₁ , Mercedes Pintado-Sierra ₂ , Félix Sánchez ₂ , Avelina Arnanz ₃ , Mercedes Boronat ₄ , Marta Iglesias ₁

Affiliation

外消旋化合物的对映选择性区分可以通过从对映纯( R )-或( S )-BINOL衍生物和1,3,5-三(1,3,5- tris )设计和制备一类新的手性共轭BINOL-多孔聚合物(CBPP)来实现。 4-苯基硼酸)苯或1,3,5-三(4-乙炔基苯基)苯、1,3,5-三乙炔基-2,4,6-三氟苯和四(4-乙炔基苯基)甲烷作为共聚单体，遵循铃木- Miyaura 和 Sonogashira-Hagihara 碳-碳耦合方法。所得CBPP具有高热稳定性、良好的比表面积和坚固的骨架，可成功应用于萜烯对映体（柠檬烯和α-蒎烯）和1-苯乙胺的荧光识别。乙腈中 CBPPs-OH 的荧光滴定表明，所有 Sonogashira 宿主都表现出对1-苯乙胺( R )-对映体的偏好，而不是 ( S )-对映体，选择性远高于相应的基于 BINOL 的可溶体系用作参考。然而，铃木宿主表现出对（ S ）-苯乙胺的偏好。关于萜烯的传感，只有 Sonogashira 宿主表现出对映体分化，几乎完全偏爱柠檬烯和 α-蒎烯的( S )-对映体。基于计算模拟和实验数据，以1-苯乙胺为分析物，手性识别是由于N·H·O氢键和主客体之间的π-π相互作用产生的独特的结合亲和力。然而，对于柠檬烯，吸附复合物的几何形状主要由 BINOL 单元的羟基与异丙烯基片段的 C=C 键之间的相互作用决定。用于制备 CBPP 的合成策略为将 BINOL 等手性中心放置在多孔聚合物中以实现对映体识别等不同手性应用提供了多种可能性。

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BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition

The enantioselective discrimination of racemic compounds can be achieved through the design and preparation of a new family of chiral conjugated BINOL–porous polymers (CBPPs) from enantiopure (R)- or (S)-BINOL derivatives and 1,3,5-tris(4-phenylboronic acid)benzene or 1,3,5-tris(4-ethynylphenyl)benzene, 1,3,5-triethynyl-2,4,6-trifluorobenzene, and tetra(4-ethynylphenyl)methane as comonomers following Suzuki–Miyaura and Sonogashira–Hagihara carbon–carbon coupling approaches. The obtained CBPPs show high thermal stability, a good specific surface area, and a robust framework and can be applied successfully in the fluorescence recognition of enantiomers of terpenes (limonene and α-pinene) and 1-phenylethylamine. Fluorescence titration of CBPPs-OH in acetonitrile shows that all Sonogashira hosts exhibit a preference for the (R)-enantiomer over the (S)-enantiomer of 1-phenylethylamine, the selectivity being much higher than that of the corresponding BINOL-based soluble system used as a reference. However, the Suzuki host reveals a preference toward (S)-phenylethylamine. Regarding the sensing of terpenes, only Sonogashira hosts show enantiodifferentiation with an almost total preference for the (S)-enantiomer of limonene and α-pinene. Based on the computational simulations and the experimental data, with 1-phenylethylamine as the analyte, chiral recognition is due to the distinctive binding affinities resulting from N···H–O hydrogen bonds and the π–π interaction between the host and the guest. However, for limonene, the geometry of the adsorption complex is mostly governed by the interaction between the hydroxyl group of the BINOL unit and the C═C bond of the iso-propenyl fragment. The synthetic strategy used to prepare CBPPs opens many possibilities to place chiral centers such as BINOL in porous polymers for different chiral applications such as enantiomer recognition.

更新日期：2022-11-23

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