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手性季铵盐催化聚联苯乙炔中超快速单手螺旋诱导及其静态螺旋手性记忆。

Ultra-fast One-Handed Helix Induction and Its Static Helicity Memory in a Poly(biphenylylacetylene) with a Catalytic Amount of Chiral Ammonium Salts.

机构信息

Graduate School of Frontier Science Initiative, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.

Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.

出版信息

Angew Chem Int Ed Engl. 2023 Apr 3;62(15):e202217020. doi: 10.1002/anie.202217020. Epub 2023 Feb 21.

Abstract

We report an ultra-fast helix induction and subsequent static helicity memory in poly(biphenylylacetylene) (PBPA-A) assisted by a catalytic amount of nonracemic ammonium salts comprised of non-coordinating tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF ) as a counter anion. The remarkable acceleration of the helix-induction rate in PBPA-A accompanied by the significant amplification of the asymmetry relies on the two methoxymethoxy groups of the biphenyl pendants, which can gain access to enfold the chiral ammoniums in a crown-ether manner in specific aromatic solvents, leading to ultra-fast helicity induction, which is completed within 30 s. In aromatic solvents, helicity memory is lost rapidly, but is quite stable in long-chain hydrocarbons. The best use of specific solvents for helicity induction and static helicity memory, respectively, provides a highly sensitive chirality sensing system toward a small amount of chiral amines and amino acids when complexed with BArF .

摘要

我们报道了在非配位四[3,5-双(三氟甲基)苯基]硼酸(BArF)作为抗衡阴离子的催化量非外消旋铵盐的辅助下,聚(联苯乙炔)(PBPA-A)中的超快螺旋诱导和随后的静态螺旋记忆。在 PBPA-A 中,螺旋诱导速率的显著加速伴随着不对称性的显著放大,这依赖于联苯侧基的两个甲氧基甲氧基,它们可以以冠醚的方式进入特定的芳香族溶剂中包裹手性铵,从而导致超快的螺旋诱导,在 30 秒内完成。在芳香族溶剂中,螺旋记忆迅速丧失,但在长链烃中非常稳定。分别使用特定溶剂进行螺旋诱导和静态螺旋记忆的最佳方法,当与 BArF 络合时,为少量手性胺和氨基酸提供了一种高灵敏度的手性传感系统。

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