[4+1]‐Cycloaddition von Benzylisonitril an cyclische Azadiensysteme des 1,2,4,5‐Tetrazins und 1,2,4‐Triazins

Yang, Xiaoguang; John, R.; Seitz, G.

doi:10.1002/ardp.2503241119

Cited by 8 publications

(1 citation statement)

References 12 publications

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“…Isocyanides react rapidly with tetrazines (rates of up to 57 M –1 s –1 in H 2 O/DMSO (4:1, v/v) at 37 °C) in a (4 + 1) cycloaddition to form 4-aminopyrazoles (Figure ). , This reaction is applicable to both labeling and release uses. Leeper et al showed that carefully selecting the structure of the isocyano reactant allows forming stable conjugates with tetrazines. − Our group recently developed biocompatible protecting groups based on this reaction.…”

Section: Introductionmentioning

confidence: 99%

Tuning Isonitrile/Tetrazine Chemistry for Accelerated Deprotection and Formation of Stable Conjugates

Deb

et al. 2019

J. Org. Chem.

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The isocyano group is a valuable functionality for bioorthogonal reactions because it rapidly reacts with tetrazines to either form stable conjugates or release payloads from 3-isocyanopropyl groups. Here we provide mechanistic insights into the dissociative steps that follow the initial cycloaddition and analyze how structural modifications affect these processes. Three main outcomes of this study have important implications for designing such groups for bioorthogonal applications. First, anion-stabilizing substituents at C-2 of the 3-isocyanopropyl group promote β-elimination and accelerate deprotection. Second, tetrazines with bulky substituents form stable imine conjugates even with primary isonitriles that are otherwise rapidly hydrolyzed. Third, the elimination step is independent from hydrolysis to the aldehyde and instead can occur directly from the imine intermediate. These findings will allow tuning the structures of tetrazine and isonitrile reactants for application in bioorthogonal ligation and release chemistry.

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Section: Introductionmentioning

confidence: 99%

Tuning Isonitrile/Tetrazine Chemistry for Accelerated Deprotection and Formation of Stable Conjugates

Deb

et al. 2019

J. Org. Chem.

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Nucleophile Singulett‐Carbene in der [4 + 1]1‐Cycloaddition mit 1,2,4,5‐Tetrazinen: Eine neue Isopyrazol‐Synthese

1993

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~ ~ ~~Nucleophilic Singlet Carbenes in the [4 + 11 Cycloaddition with 1,2,4.5-Tetrazines: a New Synthesis of Isopyrazoles A series of 3,6-disubstituted 1,2,4,5-tetrazines 6, including by subsequent [4 + 21 cycloreversion. The acceptor-substi-C6H5, SCH3, S02CH3, N(CH&, CF3, C02CH3 groups, has been tuted isopyrazole 9e is characterized as an electron-deficient submitted to [4 + 1 1 cycloaddition with the nucleophilic sin-diene by some Diels-Alder reactions with inverse electron deglet carbenes 4, 15, and 20, which are generated from the pre-mand leading to the expected azo-bridged cycloadducts 23,

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ChemInform Abstract: (4 + 1)Cycloaddition of Benzyl Isonitrile with Cyclic Azadiene Systems of 1,2,4,5‐Tetrazines and 1,2,4‐Triazines.

Yang¹,

John²,

Seitz³

1992

ChemInform

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[4+1]‐Cycloaddition von Benzylisonitril an cyclische Azadiensysteme des 1,2,4,5‐Tetrazins und 1,2,4‐Triazins

Cited by 8 publications

References 12 publications

Tuning Isonitrile/Tetrazine Chemistry for Accelerated Deprotection and Formation of Stable Conjugates

Tuning Isonitrile/Tetrazine Chemistry for Accelerated Deprotection and Formation of Stable Conjugates

Nucleophile Singulett‐Carbene in der [4 + 1]1‐Cycloaddition mit 1,2,4,5‐Tetrazinen: Eine neue Isopyrazol‐Synthese

ChemInform Abstract: (4 + 1)Cycloaddition of Benzyl Isonitrile with Cyclic Azadiene Systems of 1,2,4,5‐Tetrazines and 1,2,4‐Triazines.

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