Reactive imidazole intermediates: simplified synthetic approach to functional aliphatic cyclic carbonates

Olsson, Johan V.; Hult, Daniel; Cai, Yanling; García‐Gallego, Sandra; Malkoch, Michael

doi:10.1039/c4py00911h

Cited by 44 publications

(68 citation statements)

References 38 publications

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“…The TMC analogues are derived from substituted 1,3-propanediols through ring-closing reactions ( Figure 2-(I)) with carbonylation agents 59 such as phosgene derivatives, 60-62 bis-carbonates, 9,63 and N,N′-carbonyldiimidazole. 64 The synthesis and ROPs 3.4.1. Starting materials.…”

Section: Incorporation Of Functional Side Chainsmentioning

confidence: 99%

Poly(trimethylene carbonate)-based polymers engineered for biodegradable functional biomaterials

2016

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Aliphatic polycarbonates have drawn attention as biodegradable polymers that can be applied to a broad range of resorbable medical devices. In particular, poly(trimethylene carbonate) (PTMC), its copolymers, and its derivatives are currently studied due to their unique degradation characteristics that are different from those of aliphatic polyesters. Furthermore, their flexible and hydrophobic nature has driven the application of PTMC-based polymers to soft tissue regeneration and drug delivery. This review presents the diverse applications and functionalization strategies of PTMC-based materials in relation to recent advances in medical technologies and their subsequent needs in clinical settings.

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Section: Incorporation Of Functional Side Chainsmentioning

confidence: 99%

Poly(trimethylene carbonate)-based polymers engineered for biodegradable functional biomaterials

2016

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“…Of relevance to this study, the presence of a large (1900 Da) methoxy‐poly(ethylene glycol) substituent onto 5‐methyl, 5‐carboxylate TMC, caused ring‐chain equilibrium to dominate such that a high molecular weight polymer could not be formed with DBU as a catalyst . More recently, a DBU and 1‐(3,5‐bis(trifluoromethyl)phenyl‐3‐cyclohexyl‐2‐thiourea (TU) co‐catalyst system was reported for the ring‐opening polymerization of 1000 Da methoxy‐PEG substituted trimethylolpropane carbonate . In this latter paper, the PEG was coupled to the monomer through a carbonate linkage.…”

Section: Introductionmentioning

confidence: 99%

“…12 More recently, a DBU and 1-(3,5-bis(trifluoromethyl)phenyl-3cyclohexyl-2-thiourea (TU) co-catalyst system was reported for the ring-opening polymerization of 1000 Da methoxy-PEG substituted trimethylolpropane carbonate. 17 In this latter paper, the PEG was coupled to the monomer through a carbonate linkage. Although a relatively low molecular weight (10 kDa) polymer was targeted, a molecular weight of only 6.6 kDa was achieved along with a broad dispersity of 2.1.…”

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confidence: 99%

Homopolymerization and copolymerization kinetics of trimethylene carbonate bearing a methoxyethoxy side group

Chen

Amsden

2015

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

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The polymerization kinetics of 5‐[2‐{2‐(2‐methoxyethoxy)ethyoxy}‐ethoxymethyl]‐5‐methyl‐trimethylene carbonate (TMCM‐MOE3OM) synthesized using the organocatalyst 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) were studied and compared to those with the commonly used catalyst/initiator for ring‐opening polymerization of cyclic carbonates and esters, stannous 2‐ethylhexanoate. Further, the utility of each of these catalysts in the copolymerization of TMCM‐MOE3OM with trimethylene carbonate (TMC) and l‐lactide (LLA) was examined. Regardless of conditions with either catalyst, homopolymerization of TMCM‐MOE3OM yielded oligomers, having number average molecular weight less than 4000 Da. The resultant molecular weight was limited by ring‐chain equilibrium as well as through monomer autopolymerization. Interestingly, autopolymerization of TMC was also achieved with DBU as the catalyst. Copolymerization with TMC using stannous 2‐ethylhexanoate as the catalyst yielded random copolymers, while diblock copolymers were formed by copolymerization with LLA. With DBU as the catalyst, copolymers with LLA could not be formed, while blocky copolymers were formed with TMC. These findings should be useful in the incorporation of this monomer in the design of polymer biomaterials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 544–552

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“…MPC, owing to its facile synthesis and good stability, has become a valuable monomer in the synthesis of functional aliphatic polycarbonates. [32] To date, trifluoromethoxy-azobenzene, [33] spiropyran, [34] 2,4-dinitrobenzenesulfonyl, [35] disulfide, [36] dimethylamine, [37] benzylbenzeneboronic acid pinacol ester, [38] and 4-trifluoromethoxy-azobenzene [39] have been decorated via alkyne-azide click chemistry to develop functional aliphatic polycarbonates such as stimuli-responsive micelles as biosensors or for controlled release of hydrophobic drugs. Amphiphilic block copolymer PEG-b-PMPC could be used to construct redox-responsive, core-crosslinked micelles via click reaction with the addition of bis-(azidoethyl) disulfide.…”

Section: Alkyne-azide Reactionmentioning

confidence: 99%

Click Chemistry in Functional Aliphatic Polycarbonates

Dai

Zhang

Xia

2017

Macromol. Rapid Commun.

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Click chemistry, one of the most important methods in conjugation, plays an extremely significant role in the synthesis of functional aliphatic polycarbonates, which are a group of biodegradable polymers containing carbonate bonds in their main chains. To date, more than 75 articles have been reported on the topic of click chemistry in functional aliphatic polycarbonates. However, these efforts have not yet been highlighted. Six categories of click reactions (alkyne-azide reaction, thiol-ene reaction, Michael addition, epoxy-amine/thiol reaction, Diels-Alder reaction, and imine formation) that have been afforded for further post-polymerization modification of polycarbonates are reviewed. Through this review, a comprehensive understanding of functional aliphatic polycarbonates aims to afford insight on the design of polycarbonates for further post-polymerization modification via click chemistry and the expectation of the practical application.

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Reactive imidazole intermediates: simplified synthetic approach to functional aliphatic cyclic carbonates

Cited by 44 publications

References 38 publications

Poly(trimethylene carbonate)-based polymers engineered for biodegradable functional biomaterials

Poly(trimethylene carbonate)-based polymers engineered for biodegradable functional biomaterials

Homopolymerization and copolymerization kinetics of trimethylene carbonate bearing a methoxyethoxy side group

Click Chemistry in Functional Aliphatic Polycarbonates

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