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