Catching up with tetrazines: coordination of Re(<scp>i</scp>) to 1,2,4-triazine facilitates an inverse electron demand Diels–Alder reaction with strained alkynes to a greater extent than in corresponding 1,2,4,5-tetrazines

Sims, Mark; Kyriakou, Sotiris; Matthews, Aidan J. R.; Deary, Michael E.; Kozhevnikov, Valery N.

doi:10.1039/d3dt01451g

Cited by 5 publications

(2 citation statements)

References 16 publications

(27 reference statements)

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“…26 Another approach is to decrease the electron density on the triazine core by the coordination of heavy metal ions to the triazine core. 27,28 Yet the reactivity of triazines in iEDDA reactions with strained alkynes and trans -alkenes is generally significantly lower than that of similar tetrazines. Thus, the search for an optimal diene system for bioorthogonal iEDDA reactions continues (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Discovery of new tetrazines for bioorthogonal reactions with strained alkenes via computational chemistry

Májek,

Trtúšek

2024

RSC Adv.

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Section: Introductionmentioning

confidence: 99%

Discovery of new tetrazines for bioorthogonal reactions with strained alkenes via computational chemistry

Májek,

Trtúšek

2024

RSC Adv.

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“…For example, Lo et al demonstrated this effect in tetrazine complexes, 4 while we describesimilar behaviour of Ir(III) complexes of 1,2,4triazines. 15,16 Importantly, both the tetrazine and the triazine systems also show luminogenic behaviour in reactions with BCN derivatives. 4,15 We report the synthesis and evaluation of novel iridium(III) complexes that can participate in IEDDA reaction.…”

Section: Introductionmentioning

confidence: 99%

Annealing 1,2,4-Triazine to Iridium(III) Complexes Induces Luminogenic Behaviour in Bioorthogonal Reactions with Stain Alkynes.

Cooke,

Gristwood,

Adamson

et al. 2024

Preprint

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Phenanthroline-type ligand containing annealed 1,2,4-triazine ring was used to prepare novel Ir(III) complexes 3 and 4. The complexes are non-luminescent but show luminogenic behaviour following inverse electron demand Diels-Alder (IEDDA) reaction with bicyclononyne (BCN) derivatives. It was observed that the complex 3 reacts with BCN-C10 three times faster than the corresponding free ligand 7. The magnitude of this accelerating metal-coordination effect, however, is less profound that in previously reported Ir(III) complexes of 1,2,4-triazines in which the triazine was directly coordinated to Ir(III) metal centre. Nevertheless, luminogenic behaviour opens prospects for the use of such complexes in bioimaging applications, which was demonstrated by developing a convenient methodology using “chemistry on the complex” concept for labelling antibodies with luminescent Ir(III) complexes. Bioorthogonal reactivity of the complex 4 was then evaluated by metabolically labelling live cells with BCN groups followed by luminogenic IEDDA reaction with the triazine iridium complex.

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Bioorthogonal Cycloadditions of C3‐Trifluoromethylated 1,2,4‐Triazines with trans‐Cyclooctenes

Šlachtová,

Motornov,

Beier

et al. 2024

Chemistry A European J

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1,2,4‐triazines are a valuable class of heterodienes that can be employed in inverse electron‐demand Diels–Alder reactions. However, their broader application in bioorthogonal chemistry is limited due to their low reactivity. This article focuses on 3‐(trifluoromethyl)‐1,2,4‐triazines, which can be efficiently prepared in a one‐pot reaction from NH‐1,2,3‐triazoles. These triazines are highly reactive in reactions with strained cyclooctenes, giving second‐order rate constants as high as 230 M–1 s–1. Despite their high reactivity, the compounds remain sufficiently stable under biologically relevant conditions. We show that some of the compounds are fluorogenic, a property of potential use in bioimaging. In addition, we demonstrate the successful application of the triazines in labeling model biomolecules. Our work shows that the reactivity of 1,2,4‐triazines can be enhanced by the 3‐CF3‐substitution, which we consider an important step toward the wider use of this promising class of reagents.

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Catching up with tetrazines: coordination of Re(i) to 1,2,4-triazine facilitates an inverse electron demand Diels–Alder reaction with strained alkynes to a greater extent than in corresponding 1,2,4,5-tetrazines

Abstract: Inverse electron demand Diels Alder (IEDDA) reactions of 1,2,4-triazines are of interest to biorthogonal chemistry but suffer from slow kinetics. It is shown here that coordination of Re(I) to a...

Cited by 5 publications

References 16 publications

Discovery of new tetrazines for bioorthogonal reactions with strained alkenes via computational chemistry

Discovery of new tetrazines for bioorthogonal reactions with strained alkenes via computational chemistry

Annealing 1,2,4-Triazine to Iridium(III) Complexes Induces Luminogenic Behaviour in Bioorthogonal Reactions with Stain Alkynes.

Bioorthogonal Cycloadditions of C3‐Trifluoromethylated 1,2,4‐Triazines with trans‐Cyclooctenes

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