Direct synthesis of tetrazine functionalities on polymer backbones

Kara, Sinem Sipahioglu; Ateş, M.; Deveci, Gözde; Çetinkaya, Ahmet; Kahveci, Muhammet U.

doi:10.1002/pola.29308

Cited by 17 publications

(17 citation statements)

References 37 publications

(69 reference statements)

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“…The reaction step was shown in Scheme 2. A similar method for the synthesis of P(SAN)‐T is present in the literature [16,42] . The presence of tetrazine ring groups at 1381–1088 cm −1 is evidence of the synthesis of P(SAN)‐T [16,43] .…”

Section: Resultsmentioning

confidence: 92%

“…The peak is largely proof that the IEDDA reaction has occurred. [16] The polymer composition of the polymer was calculated using the integral ratios of the signals corresponding to the À CH 2 groups linked tetrazine group (δ = 4.2 ppm) (h) and aromatic À NH groups (δ = 9.8 ppm) (i). The IEDDA conversion was calculated as approximately 80 % by comparing the integrations of the protons i and h.…”

Section: Synthesis Of P(san)-ttco By Ieddamentioning

confidence: 99%

“…[13] Inverse Electron Demand Diels-Alder Reaction (IEDDA), namely tetrazine ligation, has high selectivity and super-fast kinetics. [14][15][16] It is defined as the reaction between an electron-poor diene (mostly 1,2,4,5-tetrazine) and an electronrich dienophile (mostly a cyclic strained olefin) to form a sixmembered ring. At the end of the reaction, N 2 gas is released, and the two molecules are clicked to each other.…”

Section: Introductionmentioning

confidence: 99%

“…The Diels‐Alder reaction was first performed in 1928 by Diels and Alder [13] . Inverse Electron Demand Diels‐Alder Reaction (IEDDA), namely tetrazine ligation, has high selectivity and super‐fast kinetics [14–16] . It is defined as the reaction between an electron‐poor diene (mostly 1,2,4,5‐tetrazine) and an electron‐rich dienophile (mostly a cyclic strained olefin) to form a six‐membered ring.…”

Section: Introductionmentioning

confidence: 99%

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Modification of Poly(Styrene‐co‐Acrylonitrile) with Tetrazine by Inverse Electron Demand Diels‐Alder Reaction

Meyvacı

Öztürk

2022

ChemistrySelect

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Poly(styrene‐co‐acrylonitrile) [P(SAN)] copolymer was obtained by using styrene and acrylonitrile monomers via free‐radical polymerization. The tetrazine groups were formed in the P(SAN) copolymer backbone by using 2‐fluorobenzyl cyanide, hydrazine hydrate, zinc iodide as the catalyst, and sodium nitrile. The tetrazine groups in the copolymer backbone were modified using trans‐cyclooctenol by the Inverse Electron Demand Diels‐Alder reaction. The spectroscopic properties of the obtained products were determined by Fourier transform infrared and proton nuclear magnetic resonance and their thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry techniques. The average molecular weights of the synthesized polymers were defined by using gel permeation chromatography method.

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Section: Resultsmentioning

confidence: 92%

Section: Synthesis Of P(san)-ttco By Ieddamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Modification of Poly(Styrene‐co‐Acrylonitrile) with Tetrazine by Inverse Electron Demand Diels‐Alder Reaction

Meyvacı

Öztürk

2022

ChemistrySelect

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“…Since our original description of the flow photoisomerization protocol, it has been employed by a number of groups for trans ‐cyclooctene synthesis with applications that include radiochemistry, cellular imaging, drug delivery and materials science . There have also been a number of modifications to the flow procedure that have been introduced.…”

Section: Figurementioning

confidence: 99%

Flow Photochemical Syntheses of trans‐Cyclooctenes and trans‐Cycloheptenes Driven by Metal Complexation

Pigga

Fox

2019

Israel Journal of Chemistry

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trans-Cyclooctenes and trans-cycloheptenes have long been the subject of physical organic study, but the broader application had been limited by synthetic accessibility. This account describes the development of a general, flow photochemical method for the preparative synthesis of trans-cycloalkene derivatives. Here, photoisomerization takes place in a closed-loop flow reactor where the reaction mixture is continuously cycled through Ag(I) on silicagel. Selective complexation of the trans-isomer by Ag(I) during flow drives an otherwise unfavorable isomeric ratio toward the transisomer. Analogous photoreactions under batch-conditions are low yielding, and flow chemistry is necessary in order to obtain trans-cycloalkenes in preparatively useful yields. The applications of the method to bioorthogonal chemistry and stereospecific transannulation chemistry are described.The unusual reactivity and well-defined chiral structure of trans-cycloalkenes has made them attractive targets for synthesis for nearly 70 years. [1][2][3] For example, trans-cyclooctene possesses planar chirality and displays a high barrier to racemization (E a = 35.6 kcal/mol), [4] and the most stable "crown" conformer has an alternating sequence of equatorial and axial hydrogens that is akin to chair cyclohexane. [5][6] The double bond of trans-cyclooctene is twisted severely in the crown conformation, [7] and as a consequence the HOMO of trans-cyclooctene is relatively high in energy. [8] trans-Cycloheptene also has a rigid structure with a distorted alkene. [7] The double bonds of medium-ring trans-alkenes are twisted. [7] trans-Cycloalkenes display unusual reactivity in HOMOalkene controlled cycloaddition reactions with dienes, [9] 1,3dipoles [8] and ketenes. [10] Strained trans-cycloalkenes also serve as ligands for transition metals. [11][12][13][14][15][16] This reactivity profile has made trans-cycloalkanes interesting targets for applications in synthesis and biology.The broadest applications of trans-cycloalkenes are in the field of bioorthogonal chemistry. The inverse-electron demand Diels-Alder reaction between tetrazines and strained alkenes has a rich history in physical organic and synthetic chemistry (Figure 1). [17][18][19] In 2008, three groups described the bioorthogonal reactions of tetrazines with strained alkenes. [20][21][22] The variant introduced by our group that used trans-cyclooctene is marked by exceptionally rapid kinetics, with rate constants that can exceed 10 6 M À 1 s À 1 in the fastest cases. [23][24] With the advances including the development of fluorogenic tetrazines [25] and reactions in live cells [26] and animals, [27] the tetrazine ligation has become a widely used tool for applications that span chemical biology, biomedical imaging, and materials science. [28][29][30][31][32][33][34][35][36][37] This account describes the development of general, flow photochemical methods for the preparative synthesis of transcycloalkene derivatives and enabled applications in synthesis and bioorthogonal chemistry. Selectiv...

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X‐yne click polymerization

Qin

Tang

2023

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Alkyne‐based click polymerizations have been nurtured into a powerful synthetic technique for the preparation of new polymers with advanced structures and versatile properties. Among them, the emerging thiol‐yne, hydroxyl‐yne, and amino‐yne click polymerizations have made remarkable progress from reactions to applications. These polymerizations avoid the usage of inherently dangerous monomers and are safer to operate than the classical azide‐alkyne click polymerization (AACP), making them more prospective for diverse applications. To greatly promote the new alkyne‐based click polymerizations beyond AACP, a new concept of “X‐yne click polymerization” is proposed to unify them, where “X” denotes the monomers that can react with alkynes under mild reaction conditions, including thiols, alcohols, amines, and other promising ones. In this review, we mainly present a brief account of the progress of X‐yne click polymerization and discuss in detail the challenges and opportunities in this field.

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Direct synthesis of tetrazine functionalities on polymer backbones

Cited by 17 publications

References 37 publications

Modification of Poly(Styrene‐co‐Acrylonitrile) with Tetrazine by Inverse Electron Demand Diels‐Alder Reaction

Modification of Poly(Styrene‐co‐Acrylonitrile) with Tetrazine by Inverse Electron Demand Diels‐Alder Reaction

Flow Photochemical Syntheses of trans‐Cyclooctenes and trans‐Cycloheptenes Driven by Metal Complexation

X‐yne click polymerization

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