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Helix-Sense Selective Polymerization: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Polymer Science
Contributor: Helena Kang

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

Advanced Polymer Synthesis and Characterization • Organic Chemistry • Chemistry • Physical Sciences

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, 10.1021/ja021233o.
  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, 10.1021/jacs.8b11628.
  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, 10.1021/ja0453533.
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