Post-polymerization modification of the side chain in optically active polymers by thiol–ene reaction

Kanbayashi, Naoya; Miyamoto, Sou; Ishido, Yuki; Okamura, Taka‐aki; Onitsuka, Kiyotaka

doi:10.1039/c6py01946c

Cited by 16 publications

(18 citation statements)

References 69 publications

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“…We previously reported a peptidic aromatic polyamide, poly “arylopeptide” ( poly-1 ), which comprises axially symmetric p -phenylene amide spacers between each residue by combining asymmetric polymerization and post-polymerization modification (Scheme a) . The CD intensity of poly-1 , which originates from the global conformation, increases nonlinearly as a function of the degree of polymerization, n , indicating cooperative convergence of plural conformers.…”

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confidence: 99%

Side-Chain-Driven Dual Structural System of Poly-Arylopeptide: Selective Helical Formation Derived from Aromatic Ring Flips on the Backbone

et al. 2019

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A methodology for producing dual structural systems of macromolecules, which involves flipping the unsymmetrical aromatic rings on the main chain is presented. Previously, we reported a non-natural polypeptide containing an aromatic ring on the peptide backbone, called a poly “arylopeptide”. Herein, we used 2,6-naphthalene rings as axially unsymmetrical spacers, which has two geometrical isomers, anti and syn, to create dual structural properties. The miniscule energy difference between the two geometrical isomers can be amplified by incorporating the 2,6-naphthylene units into the polypeptide backbone, which creates a thermodynamic driving force for the formation of two specific global structures (i.e., 31-helix or 41-helix) biased toward one side geometrical isomer depending on the side chain. Additionally, the 31-helix can be switched to the 41-helix upon addition of a small amount of additives, indicating a conformational conversion from an identical sequence. The developmental dual helical systems exploit basic molecular geometry and can serve as a design platform for synthetic polymers.

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confidence: 99%

Side-Chain-Driven Dual Structural System of Poly-Arylopeptide: Selective Helical Formation Derived from Aromatic Ring Flips on the Backbone

et al. 2019

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“…Meanwhile, it was found that the aromatic thiophenol (5) only achieved 2% conversion of alkene groups even under extended time and excessive amount of thiol compound, which could be explained by the reduced reactivity of the thiyl radical stabilized by the neighboring aromatic ring. [56,57] To illustrate the possible conjugation of bi-related thiol molecules onto our HBPs, cysteine was selected as a guest molecule [58] for thiol-ene click reaction between N-Boc-l-cysteine (4, Scheme 1) and HBP(ene) 300 -c-ene, producing HBP(ene/BocCys) 300 -c-ene/BocCys polymer. The polymer matrix HBP(ene) 300 -c-ene contained two equivalents of alkene groups per monomer unit, which reacted with 2 equiv.…”

Section: Resultsmentioning

confidence: 99%

Synthesize Hyperbranched Polymers Carrying Two Reactive Handles via CuAAC Reaction and Thiol–Ene Chemistry

Naguib

Cao

Gao

2019

Macro Chemistry & Physics

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Structurally defined hyperbranched polymers (HBPs) bearing multiple azido peripheral groups and alkene dangling groups are constructed using the authors' recently developed chain‐growth copper‐catalyzed azide‐alkyne cycloaddition polymerization (CuAACP) of an alkene‐containing AB2 monomer. Sequential integration of CuAAC and photo‐initiated thiol–ene reactions proves highly efficient and chemo‐selective functionalization of polymers at different placements with quantitative yield of both reactive groups. A variety of HBPs carrying both surface and internal functionalities are then produced, achieving quantitative/ratiometric incorporations of guest molecules in most cases. To demonstrate possible conjugation with bioactive ingredients, well‐defined HBPs decorated with peripheral cysteine moieties are produced as an example, showing pH responsiveness in water.

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“…This stereoregularity of the main chain plays a significant role in shaping the three‐dimensional structure, and in‐turn influencing the biological function of the natural macromolecules. In addition, rings are embedded in the backbones of many natural polymers, which restricts the bond rotation around the stereogenic centers . These local conformational restrictions result in a specific compact structure along the polymer backbone: that is, the six‐membered cyclic structures of cellulose and amylose backbones (Figure ) form linear and helical structures, respectively.…”

Section: Figurementioning

confidence: 99%

Functionalizable Stereocontrolled Cyclopolyethers by Ring‐Closing Metathesis as Natural Polymer Mimics

2018

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Whereas complex stereoregular cyclic architectures are commonplace in biomacromolecules, they remain rare in synthetic polymer chemistry, thus limiting the potential to develop synthetic mimics or advanced materials for biomedical applications. Herein we disclose the formation of a stereocontrolled 1,4‐linked six‐membered cyclopolyether prepared by ring‐closing metathesis (RCM). Ru‐mediated RCM, with careful control of the catalyst, concentration, and temperature, selectively affords the six‐membered‐ring cyclopolymer. Under optimized reaction conditions, no metathetical degradation, macrocycle formation, or cross‐linking was observed. Post‐polymerization modification by dihydroxylation afforded a novel polymer family encompassing a poly(ethylene glycol) backbone and sugar‐like functionalities (“PEGose”). This strategy also paves the way for using RCM as an efficient method to synthesize other stereocontrolled cyclopolymers.

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Post-polymerization modification of the side chain in optically active polymers by thiol–ene reaction

Cited by 16 publications

References 69 publications

Side-Chain-Driven Dual Structural System of Poly-Arylopeptide: Selective Helical Formation Derived from Aromatic Ring Flips on the Backbone

Side-Chain-Driven Dual Structural System of Poly-Arylopeptide: Selective Helical Formation Derived from Aromatic Ring Flips on the Backbone

Synthesize Hyperbranched Polymers Carrying Two Reactive Handles via CuAAC Reaction and Thiol–Ene Chemistry

Functionalizable Stereocontrolled Cyclopolyethers by Ring‐Closing Metathesis as Natural Polymer Mimics

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