An Axially Chiral Salicylaldehyde-Based 19F NMR Probe for the Enantiomeric Discrimination of Chiral Amines

doi:10.6023/cjoc202603044

Chinese Journal of Organic Chemistry Previous Articles Next Articles

基于轴手性水杨醛的¹⁹F NMR 探针用于手性胺的对映体辨别

彭天赐, 翁嘉劲, 谷广星, 赵延川^*

氟氮化学与先进材料国家重点实验室,上海香港化学合成联合实验室,中国科学院上海有机化学研究所,上海 200032

收稿日期:2026-03-30 修回日期:2026-05-19
基金资助:
国家自然科学基金(No.22271305,22574168)资助项目.

An Axially Chiral Salicylaldehyde-Based ¹⁹F NMR Probe for the Enantiomeric Discrimination of Chiral Amines

Tianci Peng, Jiajin Weng, Guangxin Gu, Yanchuan Zhao^*

^aState Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China

Received:2026-03-30 Revised:2026-05-19
Contact: ^*Yanchuan Zhao. E-mail:zhaoyanchuan@sioc.ac.cn

1. .pdf(1153KB)

Abstract

A concise and broadly applicable strategy for the chiral analysis of primary amines by ¹⁹F NMR remains difficult to realize because an effective probe must integrate a rigid chiral environment, a fluorinated reporter, and a reactive site for fast analyte capture. Here we report S-BINOL-probe, an axially chiral salicylaldehyde derived from BINOL and equipped with a trifluoroethoxy reporter. The probe is prepared in a short sequence from commercially available starting materials and forms diastereomeric imine adducts that display well-resolved ¹⁹F NMR signals. S-BINOL-probe discriminates 15 chiral primary amines, a broad set of amino acids, multicomponent amino acid mixtures, and representative chiral amine drugs. The same platform also enabled accurate determination of enantiomeric composition, with measured and prepared ee values showing excellent linearity. These results identify S-BINOL-probe as a synthetically accessible and analytically useful ¹⁹F NMR sensing reagent for rapid chiral analysis.

Key words: ¹⁹F NMR, Probe, Chiral analysis, Amino acids, Enantiomeric excess

Cite this article

Tianci Peng, Jiajin Weng, Guangxin Gu, Yanchuan Zhao. An Axially Chiral Salicylaldehyde-Based ¹⁹F NMR Probe for the Enantiomeric Discrimination of Chiral Amines[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202603044.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Cabré A.; Verdaguer X.; Riera A. Chem. Rev2022, 122, 269-339.
[2] (a) Peluso P.; Chankvetadze B. Chem. Rev2022, 122, 13235-13400.
(b) Coelho M. M.; Fernandes C.; Remião F.; Tiritan M. E. Molecules2021, 26, 3113.
[3] Liu H.; Wu Z.; Chen J.; Wang J.; Qiu, H. J. Chromatogr. A2023, 1708, 464367.
[4] (a) Chai Z.; Wang, W; Chen, J; Wu, Q; Ma, L; Liu, Z; Xu, G; Ling, J; Shu, Y; Liu, M; Li, C. J. Am. Chem. Soc.2026, 148, 9213-9218.
(b) Cui C.-Y.; Li B.; Zhang X.; Guo S.-L.; Pan B.-B.; Su, X.-C. J. Am. Chem. Soc.2025, 147, 19893-19901.
(c) Xu Z.; Wang C.; He S.; Wu J.; Zhao, Y. Angew. Chem. Int. Ed.2025, 64, e202417112.
(d) Chen D.; Lin Y.; Fan Y.; Li L.; Tan C.; Wang J.; Lin H.; Gao, J. Angew. Chem. Int. Ed.2023, 62, e202313753.
(e) Zhu W.; Monnie C. M.; Kitoka K.; Gronenborn, A. M. Angew. Chem. Int. Ed.2025, 64, e202419709.
(f) Meng H.; Wen L.; Xu Z.; Li, Y; Hao J.; Zhao Y. Org. Lett.2019, 21, 5206-5210.
[5] (a) Wang W.; Xia X.; Bian G.; Song L. Chem. Commun.2019, 55, 6098-6101.
(b) Weng J.; Gu G.; Zhang W.; Jia Q.; Sun Y.; Wu J.; Zhao, Y. Angew. Chem. Int. Ed.2025, 64, e202505700.
[6] Chen Y.-T.; Li B.; Chen J.-L.; Su X.-C. Analyst2023, 148, 233-238.
[7] Huang B.; Xu L.; Wang N.; Ying J.; Zhao Y.; Huang S. Anal. Chem.2022, 94, 1867-1873.
[8] Jang S.; Park H.; Duong Q. H.; Kwahk E.-J.; Kim H. Anal. Chem.2022, 94, 1441-1446.
[9] (a) Gu G.; Wang C.; Zhao Y. Synthesis2025, 57, 1671-1689.
(b) Gu G.; Xu Z.; Yu N.; Zhao, Y. Coord. Chem. Rev.2026, 551, 217454.
[10] (a) Zhou Y.; Ren Y.; Zhang L.; You L.; Yuan Y.; Anslyn E. V. Tetrahedron.2015, 71, 3515-3521.
(b) Ni C.; Zha D.; Ye H.; Hai Y.; Zhou Y.; Anslyn E. V.; You, L. Angew. Chem. Int. Ed.2018, 57, 1300-1305.
(c) You L.; Berman J. S.; Anslyn, E. V. Nat. Chem.2011, 3, 943-948.
[11] Kriegelstein M.; Profous D.; Lyčka A.; Trávníček Z.; Přibylka A.; Volná T.; Benická S.; Cankař, P. J. Org. Chem.2019, 84, 11911-11921.
[12] Dale J. A.; Mosher, H. S. J. Am. Chem. Soc.1973, 95, 512-519.
[13] (a) Jolliffe J. D.; Armstrong R. J.; Smith, M. D. Nat. Chem.2017, 9, 558-562.
(b) Pu, L. Chem. Rev2024, 124, 6643-6689.
[14] (a) Pu, L. Acc. Chem. Res.2012, 45, 150-163.
(b) Pu, L.; Senge, M. O.; Olmstead, M. M.; Power, P. P.J. Am. Chem. Soc. 1998, 120, 12682-12683.
(c) Yu, H.-B.; Hu, Q.-S.; Pu, L.J. Am. Chem. Soc. 2000, 122, 6500-6501.
(d) Pu, L.Chem. Rev. 2004, 104, 1687-1716.
[15] Li Y.; Wen L.; Meng H.; Lv J.; Luo G.; Zhao, Y. Cell Rep. Phys. Sci.2020, 1, 100100.
[16] Ma Z.; Gu G.; Zeng Y.; Weng J.; Bao W.; Zhao Y. Talanta2026, 298, 129057.
[17] (a) Li, H.; Xu, Z.; Zhang, S.; Jia, Y.; Zhao, Y. Anal. Chem. 2022, 94, 2023-2031.
(b) Dong C.; Xu Z.; Wen L.; He S.; Wu J.; Deng Q.-H.; Zhao Y. Anal. Chem.2021, 93, 2968-2973.

基于轴手性水杨醛的¹⁹F NMR 探针用于手性胺的对映体辨别

An Axially Chiral Salicylaldehyde-Based ¹⁹F NMR Probe for the Enantiomeric Discrimination of Chiral Amines

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zhongshan Xiao, Han Wang, Lu Xu, Ruijuan He, Guojing Yang, Yakun Wang, Zhaomin Liu, Tao Zhang. A Novel Phosphate-Ester-Phenothiazine Fluorescent Probe for Detection and Imaging of Sulfur Dioxide Derivatives [J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3068-3078.
[2]	Guiyuan Chen, Shengyu Li, Jilin Guo, Xiang Wang, Yetong Liu, Beining Xiao, Zhaoyang Wang. Research Progress in Synthesis and Application of 3-Cyanopyridines [J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2227-2240.
[3]	Bailin Guo, Sainü Wang, Bingxin Lei, Enju Wang. A Wash-Free Cell Membrane Fluorescent Probe Based on Monomer-Excimer Conversion [J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 2082-2089.
[4]	Jidong Zhang, Hao Wang, Xiaoxin Quan, Shenghai Zhang, Wei She. Synthesis of Aggregation-Induced Emission (AIE) Organic Polymorphs Based on Tetraphenylethene Structure: Research on Molecular Conformation and Detection Performance of Cys [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 934-940.
[5]	Lin Liu, Lulu Zhou, Tianyu Liang, Keli Zhong, Xiaomei Yan, Lijun Tang. Near-Infrared Fluorescent Probe Based on Benzopyran Derivative for Highly Sensitive Detection of SO₂ Derivative and Bioimaging [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 866-871.
[6]	Xiaofei Sun, Haiyuan Zhang, Juan Li, Ji Ma, Ruoxi Wang, Keli Zhong, Xuepeng Li, Tianyu Liang, Lijun Tang, Jianrong Li. Application of an Intelligent Integrated Platform Based on “OFF-ON” Fluorescent Probe in Salmon Freshness Monitoring [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 586-593.
[7]	Yunqiong Gu, Jiawei Yao, Zhiwei Zhong, Shuting Wen, Kun Yang, Yalu Liu, Chunfang Gan. Design, Synthesis and Antitumor Activity of Amino Acid-Modified Pregnane Derivatives [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 545-553.
[8]	Jie Yang, Qiunan She, Yicong Zhou, Liqin Kang, Jiali Zhao, Chuanxiang Liu. Cyanide-Directed Aromatic Nucleophilic Substitution of Hydrogen Reaction for Constructing Novel Naphthalimide Colorimetric Probe: Highly Sensitive Detection of Cyanide in Food and Water Samples [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 531-538.
[9]	Ke Ren, Guanglu Zhang, Yifan Niu, Xiaomeng Wang, Canyu Chen, Min Jiang. Photocatalytic Radical-Mediated Synthesis of Unnatural α-Amino Acids from Heteroaryl Aldehydes [J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 215-224.
[10]	Zhijie Jiang, Jinxiu Chen, Xiaofei Zhu, Xinhao Deng, Qiongjiao Yan, Wei Wang, Hui Zhou. Recent Advances on the Functionalization of Azlactones at Different Reactive Sites [J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 1-20.
[11]	Aopei Peng, Yang Li, Yuanyuan Zhu, Guangwen Wu, Shuangxi Gu. Advances in Chemoselective Recognition of Amino Acids by Schiff Base Fluorescent Probes [J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3301-3313.
[12]	Zhaozhou Li, Yafang Xie, Jian Tao, Xuebing Wei, Lele Li, Yajuan Li, Jiamin Tang, Huawei Niu, Xiujin Chen, Hongli Gao, Fang Li, Huichun Yu, Yunxia Yuan, Shaobin Gu, Huaibin Kang, Xiaofei Sun, Guoyan Ren, Ying Wu. Construction of Cysteine Fluorescent Probes and Their Applications in Pathological Examination [J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2335-2349.
[13]	Qing Shen, Yu Zeng, Zhonghao Li, Xiying Cao, Yuting Guo, Yunyi Ye, Zhaoyang Wang. Research Progress on Reactive Small Molecule Fluorescent Probes Based on the Formation and Cleavage of Covalent Bond [J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1194-1205.
[14]	Wenbo Zhang, Siming Su, Peng Yang. Synthesis of A Novel Calix[3]carbazole Derivative and Its Recognition and Detection of 10-Hydroxycamptothecin [J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1395-1401.
[15]	Hanyue Xiang, Shaoyin Wei, Yuji Wang, Nao Xiao. Recent Advances of Fe(II) Fluorescence Probes Based on N-Oxide Structure [J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1137-1152.

基于轴手性水杨醛的19F NMR 探针用于手性胺的对映体辨别