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Kang, H. Helix-Sense Selective Polymerization. Encyclopedia. Available online: https://encyclopedia.pub/entry/60342 (accessed on 05 October 2026).
Kang H. Helix-Sense Selective Polymerization. Encyclopedia. Available at: https://encyclopedia.pub/entry/60342. Accessed October 05, 2026.
Kang, Helena. "Helix-Sense Selective Polymerization" Encyclopedia, https://encyclopedia.pub/entry/60342 (accessed October 05, 2026).
Kang, H. (2026, September 23). Helix-Sense Selective Polymerization. In Encyclopedia. https://encyclopedia.pub/entry/60342
Kang, Helena. "Helix-Sense Selective Polymerization." Encyclopedia. Web. 23 September, 2026.
Helix-Sense Selective Polymerization
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A stereochemical polymerization in which an achiral monomer is converted into a one-handed helical polymer under the influence of a chiral catalyst, initiator, or medium is helix-sense-selective polymerization. The newly formed macromolecule is optically active because of a preferred screw sense (P or M), not because the monomer itself is chiral. Chiral rhodium catalysts polymerize achiral phenylacetylenes bearing hydroxy groups to helical polyacetylenes of preferred screw sense [1]. Air-stable palladium initiators effect living and helix-sense-selective polymerization of diazoacetates, linking molecular-weight control to helical induction [2]. Helix-sense-selective polymerization of carbodiimides and of guanidine monomers likewise produces permanently optically active helical chains when the chiral initiator sets the screw sense at the chain end [3]. The concept is a subset of asymmetric polymerization restricted to helical chirality. Polymerization of an enantiopure chiral monomer that merely inherits point chirality is not helix-sense selective unless a helical bias is additionally imposed. Racemic pairs of helices from achiral initiators lie outside the term.

helix-sense-selective polymerization helical polymers screw sense chiral catalyst

References

  1. Toshiki Aoki; Takashi Kaneko; Naoki Maruyama; Atsushi Sumi; Masahiko Takahashi; Takashi Sato; Masahiro Teraguchi; Helix-Sense-Selective Polymerization of Phenylacetylene Having Two Hydroxy Groups Using a Chiral Catalytic System. J. Am. Chem. Soc. 2003, 125, 6346-6347. [CrossRef]
  2. Jia-Hong Chu; Xun-Hui Xu; Shu-Ming Kang; Na Liu; Zong-Quan Wu; Fast Living Polymerization and Helix-Sense-Selective Polymerization of Diazoacetates Using Air-Stable Palladium(II) Catalysts. J. Am. Chem. Soc. 2018, 140, 17773-17781. [CrossRef]
  3. Hong-Zhi Tang; Paul D. Boyle; Bruce M. Novak; Chiroptical Switching Polyguanidine Synthesized by Helix-Sense-Selective Polymerization Using [(R)-3,3‘-Dibromo-2,2‘-binaphthoxy](di-tert-butoxy)titanium(IV) Catalyst. J. Am. Chem. Soc. 2005, 127, 2136-2142. [CrossRef]
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Subjects: Polymer Science
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Update Date: 23 Sep 2026
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