Architectural Control of Isosorbide-Based Polyethers via Ring-Opening Polymerization

Saxon, Derek J.; Nasiri, Mohammadreza; Mandal, Mukunda; Maduskar, Saurabh; Dauenhauer, Paul J.; Cramer, Christopher J.; LaPointe, Anne M.; Reineke, Theresa M.

doi:10.1021/jacs.9b00083

Cited by 75 publications

(59 citation statements)

References 34 publications

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“…[13][14][15][16][17] Along this direction, many biomass and CO2 derived synthetic polymers, mainly polyesters and polycarbonates, have shown their capability of establishing a circular economy of monomer-polymer-monomer. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Despite the advancement, the development of recyclable polymers under mild condition and at low energy cost have been limited.…”

Section: Introductionmentioning

confidence: 99%

Geminal Dimethyl Substitution Enables Controlled Polymerization of Penicillamine-Derived β-Thiolactones and Reversed Depolymerization

Xiong¹,

Wang²,

Dong³

et al. 2020

Preprint

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To access infinitely recyclable plastics, one key is to design thermodynamically neutral systems based on dynamic bonds for easy manipulation of the polymerization and the reverse depolymerization under low energy cost. Here, we present the controlled ring-opening polymerization of various penicillamine-derived β-thiolactones and the highly specific depolymerization of the resultant polythioesters (PNR-PenTE) for complete monomer recycling. The gem-dimethyl group confers better ROP control by reducing the activity of the chain-end thiolate groups and stabilizing the thioester linkages in the polymer backbone. High molar mass and narrow dispersity PNR-PenTE are conveniently accessible at room temperature bearing well-defined end groups and tunable side chains. PNR-PenTE can be tailored with water solubility, and/or be easily fabricated into persistent films or fibers with interesting thermal and mechanical properties. Most importantly, PNR-PenTE can be recycled to pristine enantiopure β-thiolactones at >95% conversion in a well-controlled unzipping fashion within min to hours at room temperature. Overall, this work may streamline the rapid development of a wide range of polythioesters with immense application potential as self-immolative building blocks, high value biomaterials, and sacrificial domain for nanolithography.

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Section: Introductionmentioning

confidence: 99%

Geminal Dimethyl Substitution Enables Controlled Polymerization of Penicillamine-Derived β-Thiolactones and Reversed Depolymerization

Xiong¹,

Wang²,

Dong³

et al. 2020

Preprint

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“…Therefore, a biocatalysed selective acetylation of the isosorbide endo hydroxyl represents a high yield protection step. 23,24 The transesterification has also been performed using immobilized enzymes, allowing an easy recovery of the product. However, long reaction times were generally observed to obtain complete conversion of isosorbide.…”

mentioning

confidence: 99%

“…27 As reported in Scheme 2, the first step of the synthesis was the regioselective enzymatic protection of isosorbide 2 to give the mono-acetate 5. Starting from a known protocol 24 an initial screening of the reaction conditions was made employing the supported enzyme (see Table S1, Supporting information).…”

mentioning

confidence: 99%

An Efficient and Practical Chemoenzymatic Route to (3R,3aR,6R,6aR)-Hexahydrofuro[3,2-b]furan-6-amino-3-ol (6-Aminoisomannide) from Renewable Sources

Zullo¹,

Petri²,

Iuliano³

2021

SynOpen

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The synthesis of 6-aminoisomannide is easily achieved starting from the renewable, inexpensive and commercially available isosorbide, in 66% overall yield. A biocatalysed highly regioselective acetylation of the 3-endo hydroxyl group of isosorbide was followed by the stereospecific interconversion of the 6-exo hydroxyl group into azido group, through reaction with trifluoromethanesulfonic anhydride followed by nucleophilic displacement of the triflate group by sodium azide. Finally, reduction of the azido group and deacetylation of the 3-hydroxy group were performed one pot by using LiAlH4.

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“…Notably, the synthesis of 3 is far less complicated and tedious than that of other sugar-based monomers for ROP. [13] Scheme 1. Synthesis of levoglucosenyl methyl ether 3,s tarting from levoglucosenone 1 via levoglucosenol 2,and polymerization through CROP to yield the polyacetal 4.…”

mentioning

confidence: 99%

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

2019

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The unsaturated bicyclic acetal levoglucosenyl methyl ether was readily obtained from sustainable feedstock (cellulose) and polymerized by cationic ring‐opening polymerization to produce a semicrystalline thermoplastic unsaturated polyacetal with relatively high apparent molar mass (up to ca. 36 kg mol−1) and decent dispersity (ca. 1.4). The double bonds along the chain can undergo hydrogenation and thiol–ene reactions as well as crosslinking, thus making this polyacetal potentially interesting as a reactive functional material.

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Architectural Control of Isosorbide-Based Polyethers via Ring-Opening Polymerization

Cited by 75 publications

References 34 publications

Geminal Dimethyl Substitution Enables Controlled Polymerization of Penicillamine-Derived β-Thiolactones and Reversed Depolymerization

Geminal Dimethyl Substitution Enables Controlled Polymerization of Penicillamine-Derived β-Thiolactones and Reversed Depolymerization

An Efficient and Practical Chemoenzymatic Route to (3R,3aR,6R,6aR)-Hexahydrofuro[3,2-b]furan-6-amino-3-ol (6-Aminoisomannide) from Renewable Sources

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

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