Post‐Polymerization Modifications via Active Esters

Kakuchi, Ryohei; Théato, Patrick

doi:10.1002/9783527655427.ch2

Cited by 21 publications

(19 citation statements)

References 176 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, post-polymerization modification allows for chemical transformation of commodity polyolefins into value-added materials [4], or to tailor poly(carbonate)s for specific biomedical applications [5][6][7]. A wide variety of chemoselective and/or orthogonal reactions, including thiol-ene addition [8], thiol exchange, Diels-Alder cycloaddition [9], Michael addition or reactions with active esters [10], epoxides, anhydrides, isocyanates, ketones and aldehydes, have been applied to modify functional polymer precursors [11,12].…”

Section: Introductionmentioning

confidence: 99%

Aldehyde-functional copolymers based on poly(2-oxazoline) for post-polymerization modification

Legros

Pauw‐Gillet

Tam

et al. 2015

European Polymer Journal

View full text Add to dashboard Cite

Section: Introductionmentioning

confidence: 99%

Aldehyde-functional copolymers based on poly(2-oxazoline) for post-polymerization modification

Legros

Pauw‐Gillet

Tam

et al. 2015

European Polymer Journal

View full text Add to dashboard Cite

“…As such, any deviation from an "ideal" post-modification will be significantly magnified with an increase in the degree of polymerization (DP) of the polymer, thereby making the post-modification of polymers with high molecular weight (MW) particularly difficult. An "exhaustive" post-polymerization modification reaction requires both a high degree of mechanistic fidelity and sufficient functionalization rates to prevent the production of defects, 30,31 chain scission and/or cross-linking, 26,32 since any side reaction will negatively alter the properties of the resultant polymers. Indeed, besides a number of conventional post-modification methods such as hydrolysis, 5,22,33 isocyanate chemistry, 22,23,25 activated ester chemistry, 22,23,25,34 and hydrogenation, 23 only a few types of transformations have ever advanced into the category of "exhaustive" post-modification methods, most of which are "click" reactions 35−37 and multicomponent reactions.…”

Section: Introductionmentioning

confidence: 99%

“Exhaustive” Baeyer-Villiger Oxidation of Poly(Methyl Vinyl Ketone) and Its Copolymers

Ma¹,

Cm²,

Wen-jun³

et al. 2021

Preprint

View full text Add to dashboard Cite

Poly(vinyl acetate) and its copolymers represent an important class of commodity polymers. However, the preparation of copolymers of vinyl acetate (VAc) and more activated monomers (MAMs) via copolymerization is greatly restricted due to their disparate reactivities. Issues relating to reactivity ratios remain a fundamental challenge in copolymerization. Herein, we describe a post-polymerization modification approach using poly(methyl vinyl ketone-co-MAM)s as substrates to access synthetically challenging poly(VAc-co-MAM)s. Although the direct translations of existing small-molecule Baeyer-Villiger (BV) protocols into a post-polymerization modification method failed, a mechanism-guided multi-parameter optimization on polymer substrates disclosed a set of unique “exhaustive” BV protocols which enabled a nearly quantitative functionalization without obvious chain scission or cross-linking. Furthermore, a one-pot copolymerization/“exhaustive” BV post-modification procedure was developed to produce such copolymers in a convenient and scalable manner. This user-friendly methodology is able to access diverse poly(VAc-co-MAM)s including both statistical and narrow-dispersed block copolymers and could greatly facilitate the exploration of applications with such materials.

show abstract

“…Later, Johann and co-workers introduced the aminofunctional trans-cyclooctenes (TCO) and 6-methyl-tetrazine (mTz) as initiators to obtain functional polypeptoids and performed their post-polymerization modification [104]. Postpolymerization modification (PPM) can help to overcome limitations that occur during polymerization and introduce responsive, structural and functional properties into polymers, which are otherwise incompatible with the polymerization process [36,[105][106][107][108]. PPM can offer several advantages.…”

Section: Introductionmentioning

confidence: 99%

A transient initiator for polypeptoids post-polymerization α-functionalization via activation of thioester group

Borova

Schlutt

Nickel

et al. 2021

Preprint

View full text Add to dashboard Cite

Here we introduce a post-polymerization modification method of an α-terminal functionalized poly-(N-methyl-glycine), also known as polysarcosine. We utilized 4-(methylthio)phenyl piperidine-4-carboxylate as an initiator for the ring-opening polymerization of N-methyl-glycine-N-carboxyanhydride followed by oxidation of the thioester group to yield an α-terminal reactive 4-(methylsulfonyl)phenyl piperidine-4-carboxylate polymer. This represents an activated carboxylic acid terminus, allowing straightforward modification with nucleophiles under mild reaction conditions and provides the possibility to introduce a wide variety of nucleophiles as exemplified using small molecules, fluorescent dyes and model proteins. The new initiator yielded polymers with well-defined molar mass, low dispersity and high end-group fidelity, as observed by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectroscopy. The introduced method could be of great interest for bioconjugation, but requires optimization, especially for protein conjugation.

show abstract

Post‐Polymerization Modifications via Active Esters

Cited by 21 publications

References 176 publications

Aldehyde-functional copolymers based on poly(2-oxazoline) for post-polymerization modification

Aldehyde-functional copolymers based on poly(2-oxazoline) for post-polymerization modification

“Exhaustive” Baeyer-Villiger Oxidation of Poly(Methyl Vinyl Ketone) and Its Copolymers

A transient initiator for polypeptoids post-polymerization α-functionalization via activation of thioester group

Contact Info

Product

Resources

About