Optically Active Helical Poly(phenyl isocyanide)s Bearing Achiral Benzanilide Pendants: from Controlled Synthesis to Enantioseparation Application

Jing Wang; Shuai Wang; Hai-Xu Tong; Na Liu; Zong-Quan Wu

doi:10.1007/s10118-026-3775-6

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Optically Active Helical Poly(phenyl isocyanide)s Bearing Achiral Benzanilide Pendants: from Controlled Synthesis to Enantioseparation Application

RESEARCH ARTICLE | Updated：2026-08-03

- Optically Active Helical Poly(phenyl isocyanide)s Bearing Achiral Benzanilide Pendants: from Controlled Synthesis to Enantioseparation Application
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-10(2026)
- Affiliations：
  
  a.The School of Pharmaceutical Sciences, Jilin University, Changchun 130021, China
  b.State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
- Author bio：
  
  liuna606@jlu.edu.cn (N.L.)
  zqwu@jlu.edu.cn (Z.Q.W.)
- Funds：
- DOI：10.1007/s10118-026-3775-6
  CLC：
- Received：28 May 2026，
  
  Accepted：08 June 2026，
  
  Online First：03 August 2026，
  
  Published：05 September 2026
- Accepted：
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Wang, J.; Wang, S.; Tong, H. X.; Liu, N.; Wu, Z. Q. Optically active helical poly(phenyl isocyanide)s bearing achiral benzanilide pendants: from controlled synthesis to enantioseparation application. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3775-6

Jing Wang, Shuai Wang, Hai-Xu Tong, et al. Optically Active Helical Poly(phenyl isocyanide)s Bearing Achiral Benzanilide Pendants: from Controlled Synthesis to Enantioseparation Application[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10.
Wang, J.; Wang, S.; Tong, H. X.; Liu, N.; Wu, Z. Q. Optically active helical poly(phenyl isocyanide)s bearing achiral benzanilide pendants: from controlled synthesis to enantioseparation application. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3775-6 DOI：

Jing Wang, Shuai Wang, Hai-Xu Tong, et al. Optically Active Helical Poly(phenyl isocyanide)s Bearing Achiral Benzanilide Pendants: from Controlled Synthesis to Enantioseparation Application[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10. DOI： 10.1007/s10118-026-3775-6.

摘要

Abstract

The helical structures found in biological systems

such as DNA

have inspired significant research interest in artificial helical polymers

owing to their strong potential for applications including chiral recognition and resolution

asymmetric catalysis

and other related areas. However

the preparation of single-handed helices from achiral starting materials

as well as the exploration of their chiral resolution behavior

continues to represent a considerable challenge. In this work

we present the rational design and synthesis of optically active helical poly(phenyl isocyanide)s through helix-sense selective polymerization (HSSP) of achiral phenyl isocyanide monomers

catalyzed by enantiopure Pd(II) complexes bearing

- or

-configured ligands (Pd(I

I)/L

or L

). The polymerization exhibits living and controlled characteristics

allowing for the precise modulation of molecular weights (

) with exceptionally narrow distributions (

). The resulting polymers exhibit intense optical activity and demonstrate outstanding performance in chiral recognition. Specifically

these chiral materials are utilized as a chiral stationary phase (CSP)

which can separate various racemates including

-methylbenzylamine

cobaltic acetylacetonate

and 2-hydroxy-2-phenylacetophenone. Additionally

when applied as a chiral crystallization agent

the polymer enabled the resolution of racemic

-Alanine

via

enantioselective crystallization

yielding an enantiomeric excess (

) as high as 81%.

关键词

Keywords

references

Lechner, V. M.; Nappi, M.; Deneny, P. J.; Folliet, S.; Chu, J. C. K.; Gaunt, M. J. Visible-light-mediated modification and manipulation of biomacromolecules. Chem. Rev. 2022 , 122 , 1752−1829..

Cao, J.; Zaremba, O. T.; Lei, Q.; Ploetz, E.; Wuttke, S.; Zhu, W. Artificial bioaugmentation of biomacromolecules and living organisms for biomedical applications. ACS Nano 2021 , 15 , 3900−3926..

Ikai, T.; Ando, M.; Ito, M.; Ishidate, R.; Suzuki, N.; Maeda, K.; Yashima, E. Emergence of highly enantioselective catalytic activity in a helical polymer mediated by deracemization of racemic pendants. J. Am. Chem. Soc. 2021 , 143 , 12725−12735..

Zhou, L.; He, K.; Liu, N.; Wu, Z.-Q. Recent advances in asymmetric organocatalysis based on helical polymers. Polym. Chem. 2022 , 13 , 3967−3974..

Zhou, Y.; Zhang, C.; Huang, J.; Liu, L.;Bai, J.; Li, J.; Satoh, T.; Okamoto, Y. Positive synergy between the helical poly (phenylacetylene) backbones and the helical L -proline oligopeptide pendants for enhanced enantioseparation properties. Anal. Chem. 2024 , 96 , 2078−2086..

Tilottama, B.; Vijayakrishna, K. Synthetic helical polymers: an overview on synthesis and their chiral separation efficiency. Eur. Polym. J. 2024 , 213 , 113071..

Tilottama, B.; Vijayakrishna, K. Polymers bearing covalently linked chiral proline-based pendants: induction of a highly stable helical sense that mimics double-stranded helical morphology and their chiral resolution ability. Macromolecules 2024 , 57 , 3212−3222..

Ikai, T.; Matsumoto, T.; Takeda, S.; Oki, K.; Yashima, E. Tunable synthesis of one-handed helical ladder polymers with a helical cavity or helical grooves for advanced chiral recognition. Macromolecules 2025 , 58 , 6943−6952..

Ikai, T. The dawn of chiral material developmen t using saccharide-based helical polymers. Polym. J. 2017 , 49 , 355−362..

Zhao, J.; Shi, S.; Zhang, X.; Liu, D.; Song, F.; Cheng, Y.; Li, F. Circularly polarized luminescence pyrene materials: from design to applications. Coord. Chem. Rev. 2026 , 548 , 217173..

Li, Z.-Q.; Zhang, D.-C.; Wang, H.-X.; Li, M.; Jiang, W.; Zhang, Y.; Huang, Z.; Zhong, H.; Wei, N.-X.; Dong, X.; Zhao, W.; Ji, H.; Yuan, L.; Zhou, Z.; Zhang, J.; Zhang, M.; Li, S.; Li, L.; Gu, Z.-G.; Qiu, Z.; Zhao, B.; Wang, Z.; Ma, X.; Cheng, Y.; Deng, J.; Zhang, J.; Zang, S.-Q.; Long, G.; Duan, P.; Chen, C.-F.; Zheng, Y.-X.; Zhao, Y.-S.; Luo, J.; Chen, R.; Zhuang, T.; Zhong, Y.-W.; Tang, B.-Z.; Liu, M. Circularly polarized luminescence: materials, photophysics, devices, and applications. Sci. China Chem. 2026 , 69 , 2127−2192..

Li, T.; Zhu, X.; Ouyang, G.; Liu, M. Circularly polarized luminescence from chiral macrocycles and their supramolecular assemblies. Mater. Chem. Front. 2023 , 7 , 3879−3903..

Zhao, B.; Lin, J.; Deng, J.; Liu, D. Seed-surface grafting precipitation polymerization for preparing microsized optically active helical polymer core/shell particles and their application in enantioselective crystallization. Macromol. Rapid Commun. 2018 , 39 , 1800072..

[Huang, S.; Teraguchi, M.; Kaneko, T.; Aoki, T. Preparation and enantioselective permeation of polymer membranes containing one-handed helical channels. ACS Appl. Polym. Mater . 2024 , 62049−62053..

Zhang, Y.; Deng, J.; Pan, K. Chiral helical polymer nanomaterials with tunable morphology: prepared with chiral solvent to induce helix-sense-selective precipitation polymerization. Macromolecules 2018 , 51 , 8878−8886..

Zou, H.; Wu, Q. L.; Zhou, L.; Hou, X. H.; Liu, N.; Wu, Z. Q. Chiral recognition and resolution based on helical polymers. Chinese J. Polym. Sci. 2021 , 39 , 1521−1527..

Zhao, B.; Deng, J. Emulsion polymerization of acetylenics for constructing optically active helical polymer nanoparticles. Polym. Rev. 2017 , 57 , 119−137..

Liu, L.; Zang, Y.; Jia, H.; Aoki, T.; Kaneko, T.; Hadano, S.; Teraguchi, M.; Miyata, M.; Zhang, G.; Namikoshi, T. Helix-sense-selective polymerization of achiral phenylace tylenes and unique properties of the resulting cis -cisoidal polymers. Polym. Rev. 2017 , 57 , 89−118..

Xue, Y. X.; Zhu, Y. Y.; Gao, L. M.; He, X. Y.; Liu, N.; Zhang, W. Y.; Yin, J.; Ding, Y.; Zhou, H.; Wu, Z. Q. Air-stable (phenylbuta-1, 3-diynyl)palladium (II) complexes: highly active initiators for living polymerization of isocyanides. J. Am. Chem. Soc. 2014 , 136 , 4706−4713..

Zong, Y.; Gao, R.-T.; Liu, N.; Lei, S.; Li, Z.-T.; Wu, Z.-Q. Precise synthesis of telechelic rodlike polyisocyanides: versatile building blocks for fabricating polymer frameworks with controllable pore-apertures. Chem. Sci. 2026 , 17 , 255−264..

Almeida, A. S.; Santos, R. M. G.; de Pinho, P. G.; Remião, F.; Fernandes, C. Exploring the impact of chirality of synthetic cannabinoids and cathinones: a systematic review on enantioresolution methods and enantioselectivity studies. Int. J. Mol. Sci. 2025 , 26 , 6471..

Wang, Z.; Ye, X.; Chen, Y.; Liu, Y.; Xie, S.; Tao, Y.; Zhang, J.; Wan, X. Stereoselective crystallization of chiral pharmaceuticals aided by cellulose derivatives through helical pattern matching. Chem. Eur. J. 2024 , 30 , e202401550..

Wang, Z.; Liu, Y.; Chen, Y.; Zhang, J.; Ye, X.; Wan, X. Direct crystallization resolution of racemic compounds via recognition of homochiral periodic structures using polymeric additives. Cryst. Growth Des. 2025 , 25 , 5275−5283..

Francotte, E. R. Enantioselective chromatography as a powerful alternative for the preparation of drug enantiomers. J. Chromatogr. A 2001 , 906 , 379−397..

Dong, H.; Zheng, M.; Ou, Y.; Zhang, C.; Liu, L.; Li, J.; Yang, X. A chiral stationary phase coated by surface molecularly imprinted polymer for separating 1,1‘-binaphthalene-2,2’-diamine enantiomer by high performance liquid chromatography. J. Chromatogr. A 2015 , 1376 , 172−176..

Ma, X.; Wang, M.; Li, W.; Qi, J.; Tu, S.; Zhang, L.; Wang, K. Y.; Fu, Y.; Han, Z.; Wu, X.; Zhou, H. C.; Zhu, C. An amino-acid-derived metal–organic framework with large pores for unspecific enantioseparation. J. Am. Chem. Soc. 2026 , 148 , 12024−12032..

Lin, Y.; Li, S.; Yang, H.; Mo, Q.; Lyu, S.; Luo, H.; Yang, F.; Li, X.; Xia, F. Photoresponsive and reusable chiral metal–organic framework hybrid nanochannel membrane for drug enantioseparation. ACS Appl. Mater. Interfaces 2026 , 18 , 8589−8598..

[Shen, J.; Okamoto, Y. Efficient separation of enantiomers using stereoregular chiral polymers. Chem. Rev . 2016 , 116 1094-1138.

Zhang, C.; Liu, L.; Okamoto, Y. Enantioseparation using helical polyacetylene derivatives. TrAC Trends Anal. Chem. 2020 , 123 , 115762..

Aboul-Enein, H. Y.; Kannappan, V.; Kanthiah, S. Polysaccharide and cyclodextrin-based monolithic chiral stationary phases and its application to chiral separation. Comb. Chem. High Throughput Screen. 2023 , 26 , 2583−2597..

Dhekale, N. H.; Gunjal, D. B.; Gore, A. H.; Komaravolu, Y.; Bindu, K. H.; Kolekar, G. B. Stereoselective HPLC separation of alvimopan on cellulose-based immobilized polysaccharide as a chiral stationary phase. Chirality 2018 , 30 , 982−987..

Chu, B.; Song, F.; Zou, H. Controlled synthesis of β-cyclodextrin- based starlike helical poly (phenyl isocyanide) and its application in chiral resolution. Carbohydr. Polym. 2025 , 357 , 123456..

Yuan, S.; Zhao, L.; Wang, F.; Tan, L.; Wu, D. Recent advances of optically active helical polymers as adsorbents and chiral stationary phases for chiral resolution. J. Sep. Sci. 2023 , 46 , 2300363..

Shi, G.; Dai, X.; Xu, Q.; Shen, J.; Wan, X. Enantioseparation by high-performance liquid chromatography on proline-derived helical polyacetylenes. Polym. Chem. 2021 , 12 , 242−253..

Salikolimi, K.; Praveen, V. K.; Sudhakar, A. A.; Yamada, K.; Horimoto, N. N.; Ishida, Y. Helical supramolecular polymers with rationally designed binding sites for chiral guest recognition. Nat. Commun. 2020 , 11 , 2311..

Schwartz, E.; Koepf, M.; Kitto, H. J.; Nolte, R. J. M.; Rowan, A. E. Helical poly (isocyanides): past, present and future. Polym. Chem. 2011 , 2 , 33−47..

Nolte, R. J. M. Helical poly (isocyanides). Chem. Soc. Rev. 1994 , 23 , 11..

Du, X. H.; Du, Y. N.; Ye, C. C.; Dai, S. S.; Li, G. W.; Xu, L. Synthesis of double-stranded polymers based on stereoregular rigid helical poly (phenyl isocyanide)s. Polym. Chem. 2026 , 17 , 690−696..

Wang, C.; Deng, R.; Weck, M. Orthogonal supramolecular assemblies using side-chain functionalized helical poly (isocyanide)s. Macromolecules 2023 , 56 , 3507−3516..

Xu, A.; Hu, G.; Hu, Y.; Zhang, X.; Liu, K.; Kuang, G.; Zhang, A. Remarkable structure effects on chiroptical properties of polyisocyanides carrying proline pendants. Chem. Asian J. 2013 , 8 , 2003−2014..

Deng, R.; Wang, C.; Milton, M.; Tang, D.; Hollingsworth, A. D.; Weck, M. Side-chain functionalized supramolecular helical brush copolymers. Polym. Chem. 2021 , 12 , 4916−4923..

[Liu, N.; Zhou, L.; Wu, Z. Q., Alkyne-palladium (II)-catalyzed living polymerization of isocyanides: an exploration of diverse structures and functions. Acc. Chem. Res . 2021, 54 , 3953– 3967..

Li, Y.; Kang, S. M.; Shi, G.; Chen, Y.-F.; Li, B. W.; Zhang, J.; Wan, X. H. Synthesis of proline-derived helical copolyacetylenes as chiral stationary phases for HPLC enantioseparation. Chinese J. Polym. Sci. 2025 , 43 , 61−69..

Zhou, L.; Xu, X.-H.; Jiang, Z.-Q.; Xu, L.; Chu, B.-F.; Liu, N.; Wu, Z.-Q. Selective synthesis of single-handed helical polymers from achiral monomer and a mechanism study on helix-sense-selective polymerization. Angew. Chem. Int. Ed. 2021 , 60 , 806−812..

Sun, Z.-Z.; Zhang, Y.-N.; Qiu, H.-Y.; Lu, X.-T.; Ren, L.-X.; Shen, L.-F.; Li, W.; Zhang, A. Synthesis of helical poly (phenylacetylene)s carrying dendritic pendants with varied branching densities through polymerization in different solvents. Chinese J. Polym. Sci. 2023 , 41 , 1543−1554..

Brunelli, F.; Ceresa, C.; Aprile, S.; Coppo, L.; Castiglioni, B.; Bosetti, M.; Fracchia, L.; Tron, G. C. Isocyanides in med chem: a scaffold hopping approach for the identification of novel 4-isocyanophenylamides as potent antibacterial agents against methicillin-resistant Staphylococcus aureus. Eur. J. Med. Chem. 2023 , 246 , 114950..

Klos, J.; Wurm, F.; König, H. M.; Kilbinger, A. F. M. Automated large-scale synthesis of supramolecular oligo ( p -benzamide) block copolymers. Macromolecules 2007 , 40 , 7827−7833..

[Gao, R.-T.; Kang, S.-M.; Zong, Y.; Li, T.-T.; Liu, N.; Wu, Z.-Q. Polymer frameworks with controllable pore size and chirality for enantioseparation of racemates with different sizes and chiralities. CCS Chem . 2026 , doi: 10.31635/ccschem.026.202506825..

Gao, R.-T.; Ma, Y.-Y.; Xu, Y.; Wang, J.; Liu, N.; Liu, F.; Wu, Z.-Q. Eugenol-based optically active helical polymers: from controlled synthesis to post-polymerization modification and chiral recognition. Sci. China Mater. 2026 , 69 , 2574−2582..

[Gao, B. R.; Wu, Y. J.; Xu, L.; Zou, H.; Zhou, L.; Liu, N.; Wu, Z.-Q. Synthesis of optically active helical polycarbenes through helix-sense-selective polymerization strategy and their application in chiral separation. ACS Macro Lett . 2022 , 11785−11791..

Nath, G. Y.; Samal, S.; Park, S.-Y.; Murthy, C. N.; Lee, J.-S. Induction of helicity in poly ( n -hexyl isocyanate) with terminal chiral residues. Macromolecules 2006 , 39 , 5965−5966..

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