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Kang, H. Asymmetric Polymerization. Encyclopedia. Available online: https://encyclopedia.pub/entry/60283 (accessed on 07 October 2026).
Kang H. Asymmetric Polymerization. Encyclopedia. Available at: https://encyclopedia.pub/entry/60283. Accessed October 07, 2026.
Kang, Helena. "Asymmetric Polymerization" Encyclopedia, https://encyclopedia.pub/entry/60283 (accessed October 07, 2026).
Kang, H. (2026, September 23). Asymmetric Polymerization. In Encyclopedia. https://encyclopedia.pub/entry/60283
Kang, Helena. "Asymmetric Polymerization." Encyclopedia. Web. 23 September, 2026.
Asymmetric Polymerization
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Chirality expressed at the macromolecular level through a stereochemically biased polymerization constitutes asymmetric polymerization. An achiral or prochiral monomer is converted into a polymer that is optically active because of main-chain stereocenters, a preferred helical screw sense, or both. The bias may originate in a chiral initiator or catalyst, a chiral field such as a liquid-crystalline medium, or a chiral auxiliary attached to the monomer. Helical polyacetylene formed in a chiral liquid-crystal field is a canonical illustration of field-induced asymmetric polymerization [1]. In the polymerization of 1,2-diisocyanobenzenes, a screw-sense-determining end group dictates the helical sense of the growing poly(quinoxaline-2,3-diyl) chain [2]. Asymmetric polymerization-induced crystallization-driven self-assembly of poly(aryl isocyanide) block copolymers likewise couples helical chain growth to hierarchical assembly [3]. The term is reserved for polymerization that creates macromolecular asymmetry; it is not synonymous with polymerization of an already enantiopure monomer that merely preserves point chirality, nor with racemic polymerization that yields internally compensated stereosequences.

asymmetric polymerization helical polymers screw-sense control chiral macromolecules

References

  1. Kazuo Akagi; Helical Polyacetylene: Asymmetric Polymerization in a Chiral Liquid-Crystal Field. Chem. Rev. 2009, 109, 5354-5401. [CrossRef]
  2. Michinori Suginome; Sylvain Collet; Yoshihiko Ito; Highly Effective, Easily Accessible Screw-Sense-Determining End Group in the Asymmetric Polymerization of 1,2-Diisocyanobenzenes. Org. Lett. 2002, 4, 351-354. [CrossRef]
  3. Randall A. Scanga; Ali Shahrokhinia; Jake Borges; Sean H. Sarault; Michael B. Ross; James F. Reuther; Asymmetric Polymerization-Induced Crystallization-Driven Self-Assembly of Helical, Rod-Coil Poly(aryl isocyanide) Block Copolymers. J. Am. Chem. Soc. 2023, 145, 6319-6329. [CrossRef]
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Subjects: Polymer Science
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Update Date: 23 Sep 2026
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