Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

Fu, Lei; Sui, Xuelin; Crolais, Alex E.; Gutekunst, Will R.

doi:10.1002/ange.201909172

Cited by 7 publications

(1 citation statement)

References 50 publications

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“…This is in part due to the benchtop stability and high functional group tolerance of Grubbs catalyst. With the emergence of alternative metathesis polymerizations such as cyclopolymerizations 16 , metallotropy 17 , and enyne metathesis polymerizations 18 , its surprising that the polymerization of allenes, which are known to be reactive with Grubbs catalyst, remain unexplored. 19…”

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Selective Ring Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

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2021

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Selective ring-opening allene metathesis polymerization (ROAlMP) and ruthenium vinylidene formation from 1,2-cyclononadiene (1) by simple catalyst selection are discussed. Grubbs second generation catalyst (G2) favors the formation of an alkylidene leading to the ROAlMP of (1). Grubbs first generation catalyst (G1) favors vinylidene formation and prevents the homopolymerization of (1) even at elevated temperatures. Isolation and characterization of poly(1) by NMR analysis and MALDI-TOF confirms the generation of a well-defined polyallene that exhibits good thermal stability (TD ca. 400 ºC) and fluorescent properties. Ring-opening metathesis polymerization (ROMP) of a high strained norbornene derivative (NBE-iPr) at 80 ºC using the ruthenium vinylidene generated from (1) is also investigated. The discovery of ROAlMP allows for the simple accesses of well-defined polyallenes from commercially available catalysts and will ultimately guide structure-property determinations of polyallenes.

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Selective Ring Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

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Sun²,

Moore³

2021

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Sugar‐Based Polymers from d‐Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release

et al. 2020

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Enyne monomers derived from D‐xylose underwent living cascade polymerizations to prepare new polymers with a ring‐opened sugar and degradable linkage incorporated into every repeat unit of the backbone. Polymerizations were well‐controlled and had living character, which enabled the preparation of high molecular weight polymers with narrow molecular weight dispersity values and a block copolymer. By tuning the type of acid‐sensitive linkage (hemi‐aminal ether, acetal, or ether functional groups), we could change the degradation profile of the polymer and the identity of the resulting degradation products. For instance, the large difference in degradation rates between hemi‐aminal ether and ether‐based polymers enabled the sequential degradation of a block copolymer. Furthermore, we exploited the generation of furan‐based degradation products, from an acetal‐based polymer, to achieve the release of covalently bound reporter molecules upon degradation.

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Cascade Cyclopolymerization of 5‐Ethynyl‐1,8‐Nonadiyne Derivatives to Synthesize Low Band Gap Conjugated Polyacetylenes Containing a Fused Bicyclic Structure

et al. 2022

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Cyclopolymerization is a powerful method for synthesizing polyacetylenes containing four‐ to seven‐membered rings. However, the structure of the repeat unit only consists of mono‐cycloalkene due to the single cyclization of diyne monomers. Herein, we demonstrate a novel cascade cyclopolymerization to synthesize polyacetylenes containing fused bicyclic rings from triyne monomers containing bulky dendrons via sequential cascade ring‐closing metathesis. These dendrons provided solubility and stability to the rigid bicyclic polyacetylene backbone. In addition, we controlled the regioselectivity of the catalyst approach by altering its structure and synthesized polymers containing fused bicyclo[4,3,0] or [4,4,0] rings with high molecular weights of up to 120 kg mol−1. Interestingly, the resulting polymers showed narrower band gaps (down to 1.6 eV) than polymers with mono‐cycloalkene repeat units due to the planarization of the conjugated segment resulting from the fused bicyclic structure.

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Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

Cited by 7 publications

References 50 publications

Selective Ring Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

Selective Ring Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

Sugar‐Based Polymers from d‐Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release

Cascade Cyclopolymerization of 5‐Ethynyl‐1,8‐Nonadiyne Derivatives to Synthesize Low Band Gap Conjugated Polyacetylenes Containing a Fused Bicyclic Structure

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