Synthesis of polyallenoates through copper-mediated cross-coupling of dialkynes and bis-α-diazoesters

Yu, Lefei; Zhou, Qi; Gao, Yunpeng; Fu, Zihao; Xiao, Yiyang; Li, Zi‐Chen; Wang, Jianbo

doi:10.1039/d2cc00299j

Cited by 7 publications

(5 citation statements)

References 32 publications

(17 reference statements)

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“…As these byproducts are benign precursors to intrinsically biodegradable polyesters, we could effectively transform polyolefin congeners into a recyclable polyester feedstock using mild oxidants . Furthermore, we surmised that the allene motifs in our materials would serve as critical handles for cleavage (as ozonolysis of olefins in polymers results in a complex mixture of only partially degraded products − ). In a proof-of-concept experiment, a solution of 9 55 (3.9 mg/mL in DCM) was treated with a stream of ozone at −78 °C for 3 h. t- Butyl hydroperoxide (2 equiv relative to allene) was then added, and the reaction was slowly warmed from −78 to 23 °C (see the SI).…”

Section: Resultsmentioning

confidence: 99%

Precision Synthesis of Tunable Polyallenamers from “Masked” Precursors

Galan

Brantley

2022

Macromolecules

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Incorporating reactive functional groups within polymer matrices is a promising avenue toward achieving intrinsically tunable materials. Motifs that respond to external stimuli and/or participate in a diverse array of chemical transformations are particularly enabling in the context of designing multipurpose materials. For example, polyallenamers are an emerging class of materials that exhibit stimulus-responsive behavior and are readily tailored through post-synthetic manipulations. Unfortunately, current synthetic methods for accessing these scaffolds suffer from poor control (either with respect to molecular weight or the preparation of more complex microstructures). Here, we report a new synthetic strategy that addresses these limitations by polymerizing "masked" allene precursors. Ring-opening metathesis polymerization (ROMP) of a gem-dibromobicyclo[6.1.0]non-4-ene monomer, and a subsequent Skattebøl rearrangement, afforded the target polymers in good yields (85−88%, M n = 7900−55,000 Da). Saturated congeners of these materials, which exhibit structural homology to polyolefins, could also be prepared using a simple hydrogenation protocol. Solid films of this reduced material were susceptible to photochemical tuning of bulk mechanical properties (via network formation). Moreover, our saturated polymers were readily transformed into 1,8-octandioic acid (a valuable feedstock for polyesters) using a simple ozonolysis protocol. Finally, we could leverage our synthetic strategy to prepare discrete block-like copolymer architectures with controlled allene content.

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Section: Resultsmentioning

confidence: 99%

Precision Synthesis of Tunable Polyallenamers from “Masked” Precursors

Galan

Brantley

2022

Macromolecules

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“…[23][24][25][26] In particular, isocyanide groups [27][28][29] are rather versatile building blocks that are frequently employed in the construction of heterocyclic structure decorated polymers (Scheme 1b). [30] Recently, Dong, [31,32] Li, [33,34] Tang [35][36][37][38] group and many other groups have made a significant contribution to the extension of polycycloaddition for the discovery of novel macromolecules, bearing different types of heterocycles that are constructed by classical synthetic Scheme 1. Synthetic approach for pyrrole-based polymer.…”

Section: Introductionmentioning

confidence: 99%

“…[ 23–26 ] In particular, isocyanide groups [ 27–29 ] are rather versatile building blocks that are frequently employed in the construction of heterocyclic structure decorated polymers (Scheme 1b). [ 30 ] Recently, Dong, [ 31,32 ] Li, [ 33,34 ] Tang [ 35–38 ] group and many other groups have made a significant contribution to the extension of polycycloaddition for the discovery of novel macromolecules, bearing different types of heterocycles that are constructed by classical synthetic strategies such as Ugi reaction, [ 39–41 ] Passerine reaction, [ 42–44 ] azide‐alkyne click reaction, [ 45,46 ] and A3‐coupling. [ 47 ] Surprisingly, the preparation of PBPs via direct in situ formation of pyrrole rings by polycycloaddition strategy remains unexplored.…”

Section: Introductionmentioning

confidence: 99%

Access to 2,4‐Disubstituted Pyrrole‐Based Polymer with Long‐Wavelength and Stimuli‐Responsive Properties via Copper‐Catalyzed [3+2] Polycycloaddition

Wang,

Zhang,

et al. 2024

Macromol. Rapid Commun.

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Pyrrole‐based polymers (PBPs), a type of fascinating functional polymers, play a crucial role in materials science. However, efficient synthetic strategies of pyrrole‐based polymers with diverse structures are mainly focus on conjugated polypyrroles and still remain challenging. Herein, we describe an atom and step economy protocol to access various 2,4‐disubstituted PBPs by in situ formation of pyrrole core structure via copper‐catalyzed [3+2] polycycloaddition of dialkynones and diisocyanoacetates. A series of PBPs is prepared with high molecular weight (Mw up to 18200 Da) and moderate to good yield (up to 87%), which possessed a fluorescent emission located in the green to yellow light region. Blending the PBPs with polyvinyl alcohol (PVA), the stretchable composite films exhibit a significant strengthening of the mechanical properties (tensile stress up to 59 MPa, elongation at break > 400%) and an unprecedented stress‐responsive luminescence enhancement that over fourfold fluorescent emission intensity is maintained upon stretching up to 100%. On the basis of computational studies, the unique photophysical and mechanical properties are attributed to the substitution of carbonyl chromophores on the pyrrole unit.This article is protected by copyright. All rights reserved

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“…Compared to traditional polymerization methodologies of allenes that yield alternating sp 2 - sp 3 -hybridized microstructures of limited utility, successful generation of polymeric material containing allenes has been accomplished through both cross-coupling polymerization strategies and postpolymerization modifications of polyalkenamers (Scheme ). , Although these methods impose limitations on either molecular weight or microstructural regularity, promising preliminary properties (helicity, fluorescence, degradability) of the resulting material have been demonstrated. Therefore, it is hypothesized that the generation of precision polyallenamers of appreciable size will lead to a new class of functionalizable materials with highly tailorable and adaptive properties.…”

Section: Introductionmentioning

confidence: 99%

Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity

Neary,

Zhao,

Murphy

et al. 2024

Macromolecules

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Polyallenamers represent an emerging class of polymeric materials with highly tailorable and adaptive properties. While their generation has been achieved (via crosscoupling, postpolymerization modifications, and ring opening allene metathesis polymerization (ROAlMP)), molecular weight limitations and the inability to obtain precise microstructures have prevented the ability to utilize allenes to their full potential. Herein, we demonstrate the effects that allylic derivatization of cyclic allenes (4-R-1,2-CNDs) have on the polymerization rate and regioselectivity of ROAlMP. Bulky substituents were shown to favor the formation of distal products, leading to perfectly regioregular polymerizations (>97% head-to-tail). Kinetic investigations indicated that bulky substituents also led to large polymerization rate enhancements (>20×), allowing for the generation of high molecular weight material (M n > 120 kDa) and effective chain extension. Density functional theory calculations indicate that bulky substituents destabilize the metallacyclobutane intermediate to a greater extent than the transition state (cycloreversion), leading to unprecedented rate enhancements.

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Synthesis of polyallenoates through copper-mediated cross-coupling of dialkynes and bis-α-diazoesters

Abstract: The copper-catalyzed cross-coupling of alkynes and α-diazoesters have been applied in the synthesis of polyallenoates for the first time. The polymerization tolerated various functional groups and afforded the polyallenoates with...

Cited by 7 publications

References 32 publications

Precision Synthesis of Tunable Polyallenamers from “Masked” Precursors

Precision Synthesis of Tunable Polyallenamers from “Masked” Precursors

Access to 2,4‐Disubstituted Pyrrole‐Based Polymer with Long‐Wavelength and Stimuli‐Responsive Properties via Copper‐Catalyzed [3+2] Polycycloaddition

Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity

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