<i>Endo</i> and <i>Exo</i> Diels–Alder Adducts: Temperature-Tunable Building Blocks for Selective Chemical Functionalization

Discekici, Emre H.; Amant, André H. St.; Nguyen, Shay N.; Lee, In‐Hwan; Hawker, Craig J.; Alaniz, Javier Read de

doi:10.1021/jacs.8b01544

Cited by 63 publications

(71 citation statements)

References 34 publications

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“…Polymers bearing maleimide groups are attractive scaffolds for chemical modifications as maleimide group undergoes a set of interesting reactions such as furan‐maleimide Diels–Alder reaction, anthracene‐maleimide Diels–Alder reaction, thiol‐maleimide Michael addition reaction, metal‐free azide‐maleimide 1,3‐dipolar cycloaddition click reaction, and crosslinking under photochemical and thermal conditions . Thus, there is a strong interest in the chemistry of polymers possessing maleimide functional group(s) either at the chain end(s) or as pendant groups …”

Section: Introductionmentioning

confidence: 99%

Design and Synthesis of Aromatic Polyesters Bearing Pendant Clickable Maleimide Groups

Nagane

Kuhire

Jadhav

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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A bisphenol bearing pendant maleimide group, namely, N‐maleimidoethyl‐3, 3‐bis(4‐hydroxyphenyl)‐1‐isobenzopyrrolidone (PPH‐MA) was synthesized starting from phenolphthalein. Aromatic (co)polyesters bearing pendant maleimide groups were synthesized from PPH‐MA and aromatic diacid chlorides, namely, isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), and 50:50 mol % mixture of IPC and TPC by low temperature solution polycondensation technique. Copolyesters were also synthesized by polycondensation of different molar proportions of PPH‐MA and bisphenol A with IPC. Inherent viscosities and number‐average molecular weights of aromatic (co)polyesters were in the range of 0.52–0.97 dL/g and 20,200–32,800 g/mol, respectively indicating formation of medium to reasonably high‐molecular‐weight polymers. 13C NMR spectral analysis of copolyesters revealed the formation of random copolymers. The 10% weight loss temperature of (co)polyesters was found in the range 470–484 °C, indicating their good thermal stability. A selected aromatic polyester bearing pendant maleimide groups was chemically modified via thiol‐maleimide Michael addition reaction with two representative thiol compounds, namely, 4‐chlorothiophenol and 1‐adamantanethiol to yield post‐modified polymers in a quantitative manner. Additionally, it was demonstrated that polyester containing pendant maleimide groups could be used to form insoluble crosslinked gel in the presence of a multifunctional thiol crosslinker. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 630–640

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Section: Introductionmentioning

confidence: 99%

Design and Synthesis of Aromatic Polyesters Bearing Pendant Clickable Maleimide Groups

Nagane

Kuhire

Jadhav

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…The excellent Michael‐acceptor properties of maleimides required the protection of their C=C bond in form of the Diels–Alder adduct 13 in order to prevent side reactions with Ph 3 P, which is needed as a reagent in the Mitsunobu transformation. The endo ‐isomer of 13 was chosen over the exo ‐isomer, because it provides sufficient retro‐Diels–Alder reactivity already at 60 °C (see Supporting Information, Section 2.2.4) instead of 150 °C, which is necessary for the cleavage of the exo ‐adduct of 13 . The deprotection at 60 °C is compatible with the thermal stability of the radical center, which is crucial for the final deprotection to 9 .…”

Section: Resultsmentioning

confidence: 99%

SLIM: A Short‐Linked, Highly Redox‐Stable Trityl Label for High‐Sensitivity In‐Cell EPR Distance Measurements

et al. 2020

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The understanding of biomolecular function is coupled to knowledge about the structure and dynamics of these biomolecules,p referably acquired under native conditions.I nt his regard, pulsed dipolar EPR spectroscopy( PDS) in conjunction with site-directed spin labeling (SDSL) is an important method in the toolbox of biophysical chemistry. However,t he currently available spin labels have diverse deficiencies for in-cell applications,f or example,l ow radical stability or long bioconjugation linkers.Inthis work, asynthesis strategy is introduced for the derivatization of trityl radicals with am aleimide-functionalized methylene group.T he resulting trityl spin label, called SLIM, yields narrowd istance distributions,e nables highly sensitive distance measurements down to concentrations of 90 nm,a nd shows high stability against reduction. Using this label, the guanine-nucleotide dissociation inhibitor (GDI) domain of Yersinia outer protein O( YopO) is shown to changei ts conformation within eukaryotic cells.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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“…Maleimides also undergo [4 + 2] cycloadditions with furan derivatives to afford oxanorbornenes. This provides a simple strategy to protect maleimides as, conversely to the norbornene products, it is a thermally reversible reaction as the retro‐Diels Alder reaction of oxanorbornenes occurs at reasonable temperature . The Diels‐Alder reaction between 1 and furan was performed under similar experimental conditions (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Inverse electron‐demand Diels‐Alder (iEDDA) bioorthogonal conjugation of half‐sandwich transition metallocarbonyl entities to a model protein

Jamroz

Fischer‐Durand

Palusiak

et al. 2020

Applied Organom Chemis

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Novel transition metallocarbonyl complexes carrying a norbornene or an oxanorbornene group were synthesized by [4 + 2] cycloaddition between the organometallic maleimide dienophiles and cyclopentadiene or furan, respectively. The oxanorbornene adduct was obtained as a mixture of endo and exo isomers as confirmed by X‐ray diffraction and NMR spectroscopy. The (oxa)norbornene groups further provided convenient chemical reporters to carry out inverse electron demand Diels‐Alder (iEDDA) reactions with tetrazine derivatives. Detailed kinetic studies with a model tetrazine revealed that faster rates of reaction were determined with both isomers of the oxanorbornene complex with respect to the norbornene complexes. Eventually, incorporation of metallocarbonyl entities into bovine serum albumin equipped with tetrazine handles was achieved as shown by IR spectroscopy of the protein conjugates.

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Endo and Exo Diels–Alder Adducts: Temperature-Tunable Building Blocks for Selective Chemical Functionalization

Cited by 63 publications

References 34 publications

Design and Synthesis of Aromatic Polyesters Bearing Pendant Clickable Maleimide Groups

Design and Synthesis of Aromatic Polyesters Bearing Pendant Clickable Maleimide Groups

SLIM: A Short‐Linked, Highly Redox‐Stable Trityl Label for High‐Sensitivity In‐Cell EPR Distance Measurements

Inverse electron‐demand Diels‐Alder (iEDDA) bioorthogonal conjugation of half‐sandwich transition metallocarbonyl entities to a model protein

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