Protected thiol strategies in macromolecular design

Goethals, Fabienne; Frank, Daniel; Prez, Filip Du

doi:10.1016/j.progpolymsci.2016.09.003

Cited by 73 publications

(71 citation statements)

References 273 publications

(311 reference statements)

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“…In order to prepare star polymers, Core 1 was subjected to reaction with 2a and 2b which contain masked thiol group (Scheme ). Free thiols were generated in situ due to the known propensity of aliphatic thiols to undergo oxidation in the presence of air leading to formation of disulfide . The unmasking reaction was carried out under inert atmosphere in the presence of LiOH as a base.…”

Section: Resultsmentioning

confidence: 99%

A New Approach for the Synthesis of Miktoarm Star Polymers Through a Combination of Thiol–Epoxy “Click” Chemistry and ATRP/Ring‐Opening Polymerization Techniques

Gadwal

Wadgaonkar

Ichake

et al. 2018

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

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A new approach was developed for synthesis of certain A3B3‐type of double hydrophilic or amphiphilic miktoarm star polymers using a combination of “grafting onto” and “grafting from” methods. To achieve the synthesis of desired miktoarm star polymers, acetyl protected poly(ethylene glycol) (PEG) thiols (Mn = 550 and 2000 g mol−1) were utilized to generate A3‐type of homoarm star polymers through an in situ protective group removal and a subsequent thiol–epoxy “click” reaction with a tris‐epoxide core viz. 1,1,1‐tris(4‐hydroxyphenyl)ethane triglycidyl ether. The secondary hydroxyl groups generated adjacent to the core upon the thiol–epoxy reaction were esterified with α‐bromoisobutyryl bromide to install atom transfer radical polymerization (ATRP) initiating sites. ATRP of N‐isopropylacrylamide (NIPAM) using the three‐arm star PEG polymer fitted with ATRP initiating sites adjacent to the core afforded A3B3‐type of double hydrophilic (PEG)3[poly(N‐isopropylacrylamide)] (PNIPAM)3 miktoarm star polymers. Furthermore, the generated hydroxyl groups were directly used as initiator for ring‐opening polymerization of ε‐caprolactone to prepare A3B3‐type of amphiphilic (PEG)3[poly(ε‐caprolactone)]3 miktoarm star polymers. The double hydrophilic (PEG)3(PNIPAM)3 miktoarm star polymers showed lower critical solution temperature around 34 °C. The preliminary transmission electron microscopy analysis indicated formation of self‐assembly of (PEG)3(PNIPAM)3 miktoarm star polymer in aqueous solution. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 146–156

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Section: Resultsmentioning

confidence: 99%

A New Approach for the Synthesis of Miktoarm Star Polymers Through a Combination of Thiol–Epoxy “Click” Chemistry and ATRP/Ring‐Opening Polymerization Techniques

Gadwal

Wadgaonkar

Ichake

et al. 2018

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

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“…Thiolactone chemistry has already been well reported as a highly useful tool for polymer functionalization and post‐modification . It circumvents many of the problems that arise from directly using thiols such as poor commercial availability, short shelf‐life, and unpleasant smell . The ring‐opening of homocysteine‐γ‐thiolactone with a primary amine releases the protected thiol, which can then undergo a subsequent in situ Michael addition with, for example, an acrylate or an acrylamide .…”

Section: Methodsmentioning

confidence: 99%

Automated Synthesis Protocol of Sequence‐Defined Oligo‐Urethane‐Amides Using Thiolactone Chemistry

Holloway

Mertens

Prez

et al. 2018

Macromol. Rapid Commun.

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An automated, iterative protocol for the synthesis of multifunctional, sequence‐defined oligo‐urethane‐amides using thiolactone chemistry is reported. Here, sequenced functionalization of the backbone is easily introduced using commercially available primary amines. The chemistry is carried out on solid phase using different supports for better optimization of the synthetic protocol and in order to demonstrate the versatility of the approach. This technique is very effective for iterative synthesis and solid‐phase chemistry and enables the exploration of full automation of this approach using a robotic peptide synthesizer. As a result, this automated protocol allows for the synthesis of a sequence‐defined nonamer of high purity.

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“…[44,70] RAFT polymerization is another versatile polymerization technique yielding well-defined polymers, which offerss everal routes for the introductionofdisulfide bondsand thiol reactive moieties. [65,71,72] Disulfide bonds can be incorporated by selfcondensing vinyl polymerization of disulfide monomers, yielding hyperbranched architectures with bioreducible moieties. [73][74][75] Further, cross-linkingm onomers containing disulfide bonds can be implemented in numerous RAFT crosslinking polymerization strategies, [76] for example, in arm-first nanogel formation [77][78][79] or core-first approaches.…”

Section: Structurementioning

confidence: 99%

Of Thiols and Disulfides: Methods for Chemoselective Formation of Asymmetric Disulfides in Synthetic Peptides and Polymers

Schäfer

Barz

2018

Chemistry A European J

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In protein or peptide chemistry, thiols are frequently chosen as a chemical entity for chemoselective modification reactions. Although it is a well-established methodology to address cysteines and homocysteines in aqueous media to form S-C bonds, possibilities for the chemoselective formation of asymmetric disulfides have been less approached. Focusing on bioreversibility in conjugation chemistry, the formation of disulfide bonds is highly desirable for the attachment of thiol-containing bioactive agents to proteins or in cross-linking reactions, because disulfide bonds can combine stability in blood with degradability inside cells. In this Concept article, recent approaches in the field of activating groups for thiol moieties incorporated in peptide and polymer materials are highlighted. Advantageous combinations of stability during synthesis of the material with high reactivity towards thiols are explored focusing on simplification and prevention of side reactions as well as additional deprotection and activation steps prior to disulfide formation. Moreover, applications of this chemistry are highlighted and future perspectives are envisioned.

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Protected thiol strategies in macromolecular design

Cited by 73 publications

References 273 publications

A New Approach for the Synthesis of Miktoarm Star Polymers Through a Combination of Thiol–Epoxy “Click” Chemistry and ATRP/Ring‐Opening Polymerization Techniques

A New Approach for the Synthesis of Miktoarm Star Polymers Through a Combination of Thiol–Epoxy “Click” Chemistry and ATRP/Ring‐Opening Polymerization Techniques

Automated Synthesis Protocol of Sequence‐Defined Oligo‐Urethane‐Amides Using Thiolactone Chemistry

Of Thiols and Disulfides: Methods for Chemoselective Formation of Asymmetric Disulfides in Synthetic Peptides and Polymers

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