Helical, Chiral Polyisocyanides Bearing Ferrocenyl Groups as Pendants: Synthesis and Properties

Hida, Noriyuki; Takei, Fumio; Onitsuka, Kiyotaka; Shiga, Kiyoshi; Asaoka, Sadayuki; Iyoda, Tomokazu; Takahashi, Shigetoshi

doi:10.1002/anie.200351456

Cited by 65 publications

(27 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This compares with the single redox couple observed in a ferrocene-containing poly(isocyanide) in which the chiral center was located somewhat closer to the skeleton of the polymer. 53 It is hoped that the chiral polymer 20 will show intramacromolecule transport in a chiral form, and therefore act as a molecular solenoid. 54 …”

Section: Preparation Of Functional Polymersmentioning

confidence: 99%

Long‐range effects of chirality in aromatic poly(isocyanide)s

Amabilino

Serrano

Sierra

et al. 2006

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

The preparation of optically active atropoisomeric polymers which present chiral backbones, thanks to induction during their synthesis from stereogenic centers, located far away from the skeleton is possible, thanks principally to semirigid conformations of the promesogenic spacers between them. The result is that chiral “information” can be passed as far as 21 Å from the asymmetric center to the carbon atom that forms the polymeric chain in poly(isocyanide)s. The sense of chiral induction in these conformationally rigid polymers parallels the helical sense of the cholesteric phases, as well as to the helical senses of chiral smectic C phases, induced by the monomers in nematic and smectic C phases, respectively. All these phenomena obey the odd–even rules proposed for chiral sense changes in these liquid crystalline phases. Noncovalent interactions play an important part in the induction process, in which steric arguments can be used to justify the inductions observed. The methodology can be used to prepare macromolecules, which display switching behavior upon thermal or electrochemical stimulus. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3161–3174, 2006

show abstract

Section: Preparation Of Functional Polymersmentioning

confidence: 99%

Long‐range effects of chirality in aromatic poly(isocyanide)s

Amabilino

Serrano

Sierra

et al. 2006

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

show abstract

“…) . Analysis by UV–vis spectroscopy of Poly‐1 and Poly‐4 in THF shows the expected absorbance around 255 nm in both parent polymer and conjugate which is attributable to the phenyl side‐chains of the polymer . A new absorbance around 226 nm for the polymer conjugate can be seen and is suspected to be the result of absorbance from the peptide backbone.…”

Section: Resultsmentioning

confidence: 99%

End‐group functionalization and postpolymerization modification of helical poly(isocyanide)s

Croom

Tarallo

Weck

2016

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

This contribution presents the synthesis of helical alkyne‐terminated polymers using a functionalized Nickel complex to initiate the polymerization of menthylphenyl isocyanides. The resulting polymers display low dispersities and controlled molecular weights. Copper‐catalyzed azide/alkyne cycloadditions (CuAAC) are performed to attach various azide‐containing compounds to the polymer termini. After azido‐phosphonate moiety attachment the polymer displays a signal at 25.4 ppm in the 31P NMR spectrum demonstrating successful end‐group functionalization. End‐group functionalization of a fluorescent dye allows to determine the functionalization yield as 89% (±8). Successful ligation of an azide‐functionalized peptide sequence (MKLA = 1547 g/mol) increases the Mn from 5100 for the parent polymer to 6700 for the bioconjugate as visualized by GPC chromatography. Analysis by CD spectroscopy confirms that the helical conformation of the poly(isocyanide) block in the peptide–polymer conjugate is maintained after postpolymerization modification. These results demonstrate an easy, generalizable, and versatile strategy toward mono‐telechelic helical polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2766–2773

show abstract

“…Poly(isocyanide)bearing porphyrins, which are sterically bulky substituent groups, as a pendant groups were readily prepared ( Incorporated porphyrin units were regularly arranged, which provided interesting optical properties. Ferrocene-containing poly(isocyanide)s 35a and 35b were also prepared with dinuclear Pd-Pt complex 29 (Scheme 8.16) [37]. A series of tribrock copolymers 34a-f, in which porphyrin units were introduced as pendant groups in the central part of the main chain, were prepared by living polymerization in the presence of a Pd-Pt m-ethynediyl initiator 29 [36].…”

Section: Synthesis Of Poly(isocyanide)s Having Chiral Aryl Pendantsmentioning

confidence: 99%

Poly(isocyanide)s, Poly(quinoxaline‐2,3‐diyl)s, and Related Helical Polymers Used as Chiral Polymer Catalysts in Asymmetric Synthesis

Nagata

Suginome

2011

Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis

View full text Add to dashboard Cite

Helical, Chiral Polyisocyanides Bearing Ferrocenyl Groups as Pendants: Synthesis and Properties

Abstract: Recent developments in polymer synthesis have provided us with new methods for preparing nano-sized polymer molecules with precisely controlled chemical sequence, molecular weight, and stereostructure, as well as molecular shape.

Cited by 65 publications

References 28 publications

Long‐range effects of chirality in aromatic poly(isocyanide)s

Long‐range effects of chirality in aromatic poly(isocyanide)s

End‐group functionalization and postpolymerization modification of helical poly(isocyanide)s

Poly(isocyanide)s, Poly(quinoxaline‐2,3‐diyl)s, and Related Helical Polymers Used as Chiral Polymer Catalysts in Asymmetric Synthesis

Contact Info

Product

Resources

About