Multifunctional poly(phosphoester)s with two orthogonal protective groups

Müller, Laura; Steinbach, Tobias; Wurm, Frederik R.

doi:10.1039/c5ra07167d

Cited by 29 publications

(7 citation statements)

References 34 publications

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“…The 31 P{H} NMR spectrum showed a singlet at 17.90 ppm, typical for cyclic phosphate monomers. 27,28 Fig . 1 (a) SEC elugrams of all co-and terpolymers (in DMF, RI signal), (b) DSC thermograms of all co-and terpolymers (heating and cooling rate 10 K min −1 , 1 st run).…”

Section: Monomer Synthesesmentioning

confidence: 99%

Surface-attached poly(phosphoester)-hydrogels with benzophenone groups

Becker

Deng²,

Zober³

et al. 2018

Polym. Chem.

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Section: Monomer Synthesesmentioning

confidence: 99%

Surface-attached poly(phosphoester)-hydrogels with benzophenone groups

Becker

Deng²,

Zober³

et al. 2018

Polym. Chem.

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“…With similar strategies now available for polyphosphonates too, there is a wide range of chemical functionality possible. As some functional groups may be incompatible with the ROP procedure, strategies for facile post‐polymerization polymerization have also been developed, leading to multifunctional polymers, for example the introduction of orthogonal protective groups . A further approach entails the addition of vinyl moieties, which can undergo further reactions into acetals, thioacetals or undergo thiol‐ene addition reactions, as well as alkyne groups for the introduction of functionality via azide click chemistry …”

Section: Synthesismentioning

confidence: 99%

“…As some functional groups may be incompatible with the ROP procedure, strategies for facile post-polymerization polymerization have also been developed, leading to multifunctional polymers, for example the introduction of orthogonal protective groups. [75] A further approach entails the addition of vinyl moieties, [76] which can undergo further reactions into acetals, thioacetals or undergo thiol-ene addition reactions, as well as alkyne groups for the introduction of functionality via azide click chemistry. [31] An alternative route to high molecular weight polyphosphoesters is metathesis, through functionalization of phosphate monomers with functional groups containing unsaturated bonds ( Figure 12).…”

Section: Polyphosphoester Synthesismentioning

confidence: 99%

Branched Macromolecular Architectures for Degradable, Multifunctional Phosphorus‐Based Polymers

Henke

Brüggemann

Teasdale

2017

Macromol. Rapid Commun.

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This feature article briefly highlights some of the recent advances in polymers in which phosphorus is an integral part of the backbone, with a focus on the preparation of functional, highly branched, soluble polymers. A comparison is made between the related families of materials polyphosphazenes, phosphazene/phosphorus-based dendrimers and polyphosphoesters. The work described herein shows this to be a rich and burgeoning field, rapidly catching up with organic chemistry in terms of the macromolecular synthetic control and variety of available macromolecular architectures, whilst offering unique property combinations not available with carbon backbones, such as tunable degradation rates, high multi-valency and facile post-polymerization functionalization. As an example of their use in advanced applications, we highlight some investigations into their use as water-soluble drug carriers, whereby in particular the degradability in combination with multivalent nature has made them useful materials, as underlined by some of the recent studies in this area.

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“…The structural similarity of PEPs and nucleic and teichoic acids favors the use of these polymers in future biomedical materials [1,2,3,4,5,6,7,8,9]. Ring-opening polymerization (ROP) of cyclic ethylene phosphate monomers (CEPMs) is an efficient method for the preparation of PEPs (Scheme 1a) [10,11,12,13,14,15]. Recently, we demonstrated the high efficiency of BHT-Mg (BHT = 2,6-di- tert -butyl-4-methylphenolate) alkoxy complexes ( Mg1 , Scheme 1b) in the ROP of ethylene phosphates with the formation of linear and branched polymers [16,17,18].…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights of BHT-Mg-Catalyzed Ethylene Phosphate’s Coordination Ring-Opening Polymerization: DFT Modeling and Experimental Data

et al. 2018

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Poly(ethylene phosphates) are promising polymers for use in biomedical applications. Catalytic ring-opening polymerization (ROP) of cyclic ethylene phosphate monomers (CEPMs) is the most effective approach for obtaining these polymers. The mechanism of coordination ROP of CEPMs remains unclear. We report, for the first time, the results of DFT modeling of CEPM ROP. In these calculations by Gaussian-09 program package with the B3PW91/DGTZVP basis set, we explored methyl ethylene phosphate (MeOEP) ROP catalyzed by dimeric and monomeric catalytic species derived from heteroleptic complex [(BHT)Mg(μ-OBn)(THF)]2 (Mg1, BHT = 2,6-di-tert-butyl-4-methylphenolate). Analysis of the reaction profiles for the binuclear and mononuclear reaction mechanisms allowed us to conclude that the ROP of MeOEP is preferentially catalyzed by mononuclear Mg complexes. This estimation was confirmed by comparative polymerization experiments using MeOEP and traditional monomers ε-caprolactone (εCL), racemic lactide (rac-LA), and l-lactide (l-LA) initiated by Mg1. ROP of MeOEP proceeds at an extremely high rate due to the substantially lower activation barrier calculated for mononuclear mechanism in comparison with that of cyclic esters that polymerize without the dissociation of BHT-Mg binuclear species. We also demonstrated the use of MeOEP as a "monomerization" agent in the synthesis of MeOEP-lactide block copolymers. Comparison of the multiple acceleration of l-LA ROP after MeOEP prepolymerization and formation of atactic PLA blocks in rac-LA polymerization with the heterotactic PLA formation during Mg1-catalyzed homopolymerization also confirmed the mononuclear nature of the polyphosphate-containing catalytic particles.

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Multifunctional poly(phosphoester)s with two orthogonal protective groups

Abstract: 2-(2-(Benzyloxy)ethoxy)-1,3,2-dioxaphospholane-2-oxide was developed for the ring-opening polymerization to multifunctional poly(phosphoester)s. An acetal-protected comonomer allows selective release of the hydroxyl groups by hydrolysis and hydrogenation.

Cited by 29 publications

References 34 publications

Surface-attached poly(phosphoester)-hydrogels with benzophenone groups

Surface-attached poly(phosphoester)-hydrogels with benzophenone groups

Branched Macromolecular Architectures for Degradable, Multifunctional Phosphorus‐Based Polymers

Mechanistic Insights of BHT-Mg-Catalyzed Ethylene Phosphate’s Coordination Ring-Opening Polymerization: DFT Modeling and Experimental Data

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