Polyarylisocyanides Derived from an Alkyne-Pd(II) Catalyst as Robust Alignment Media with Excellent Enantiodiscimination

The development of chiral alignment media for measuring anisotropic NMR parameters provides an opportunity to determine the absolute configuration of chiral molecules without the need for derivatization. However, chiral alignment media with a high and robust enantiodiscriminating property for a wide...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2023-12, Vol.95 (51), p.18850-18858
Main Authors: Li, Gao-Wei, Wang, Xiao-Juan, Shi, Shuai-Hua, Liu, Lan-Tao, Li, Jia-Qian, Sun, Han, Wu, Zong-Quan, Lei, Xinxiang
Format: Article
Language:English
Subjects:
Absolute configuration
Alignment
Alkynes
Anisotropy
Catalysts
Cholesterol
Crystals
Dichloromethane
Dipole interactions
Handedness
Helices
Liquid crystals
NMR
Nuclear magnetic resonance
Robustness
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Summary:The development of chiral alignment media for measuring anisotropic NMR parameters provides an opportunity to determine the absolute configuration of chiral molecules without the need for derivatization. However, chiral alignment media with a high and robust enantiodiscriminating property for a wide range of chiral molecules are still scarce. In this study, we synthesized cholesterol-end-functionalized helical polyisocyanides from a chiral monomer using a cholesterol-based alkyne-Pd­(II) initiator. These stereoregular polyisocyanides form stable and weak anisotropic lyotropic liquid crystals (LLCs) in dichloromethane systems, exhibiting highly optical activities in both single left- and right-handed helices. The preparation process of the media was straightforward, and the aligning property of the LLCs could be controlled by adjusting the concentration and temperature. Using the chiral polyisocyanides, we extracted the residual dipolar coupling for an enantiomeric pair of isopinocampheol (IPC), as well as a number of pharmaceutical molecules, demonstrating excellent enantiodiscriminating properties for a broad range of chiral compounds.
ISSN:0003-2700
1520-6882
DOI:10.1021/acs.analchem.3c04240