Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis

John-Paul O'Shea; Vera Solovyeva; Xianrong Guo; Junpeng Zhao; Nikos Hadjichristidis; Valentin Rodionov

doi:10.1039/c3py01368e

Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis

John-Paul O'Shea, Vera Solovyeva, Xianrong Guo, Junpeng Zhao, Nikos Hadjichristidis, Valentin Rodionov

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

A number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal "click" chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is © 2014 The Royal Society of Chemistry.

Original language	English (US)
Pages (from-to)	698-701
Number of pages	4
Journal	Polym. Chem.
Volume	5
Issue number	3
DOIs	https://doi.org/10.1039/c3py01368e
State	Published - 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Funding from KAUST OCRF (award project "Catalysis With Soft Materials") is acknowledged with thanks.

ASJC Scopus subject areas

Biochemistry
Organic Chemistry
Biomedical Engineering
Bioengineering
Polymers and Plastics

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title = "Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis",

abstract = "A number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal {"}click{"} chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is {\textcopyright} 2014 The Royal Society of Chemistry.",

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note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Funding from KAUST OCRF (award project {"}Catalysis With Soft Materials{"}) is acknowledged with thanks.",

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T1 - Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis

AU - O'Shea, John-Paul

AU - Solovyeva, Vera

AU - Guo, Xianrong

AU - Zhao, Junpeng

AU - Hadjichristidis, Nikos

AU - Rodionov, Valentin

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Funding from KAUST OCRF (award project "Catalysis With Soft Materials") is acknowledged with thanks.

PY - 2014

Y1 - 2014

N2 - A number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal "click" chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is © 2014 The Royal Society of Chemistry.

AB - A number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal "click" chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is © 2014 The Royal Society of Chemistry.

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Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis

Abstract

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ASJC Scopus subject areas

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