Fluorous Analogue of Chloramine-T: Preparation, X-ray Structure Determination, and Use as an Oxidant for Radioiodination and s-Tetrazine Synthesis

Dzandzi, James P. K.; Beckford-Vera, Denis; Genady, Afaf R.; Albu, Silvia; Eltringham-Smith, Louise J.; Capretta, Alfredo; Sheffield, William P.; Valliant, John F.

doi:10.1021/acs.joc.5b00988

Cited by 14 publications

(4 citation statements)

References 70 publications

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“…Similarly, F-CAT could oxidize the amino substituted dipyridine-tetrazine with 86% yield and the product could be easily separated through fluorous solid-phase extraction. 101,102 Alternatively, by using photocatalysts, the dihydrotetrazine could be oxidized to tetrazine in quantitative yields with 660 nm LED in the presence of methylene blue within 200 s. Even under ambient light, the photoredox reaction could be afforded in 47% conversion in 2 h (Fig. 12b).…”

Section: Synthesis Of Tetrazine Derivativesmentioning

confidence: 99%

Inverse electron demand Diels–Alder reactions in chemical biology

2017

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The emerging inverse electron demand Diels-Alder (IEDDA) reaction stands out from other bioorthogonal reactions by virtue of its unmatchable kinetics, excellent orthogonality and biocompatibility. With the recent discovery of novel dienophiles and optimal tetrazine coupling partners, attention has now been turned to the use of IEDDA approaches in basic biology, imaging and therapeutics. Here we review this bioorthogonal reaction and its promising applications for live cell and animal studies. We first discuss the key factors that contribute to the fast IEDDA kinetics and describe the most recent advances in the synthesis of tetrazine and dienophile coupling partners. Both coupling partners have been incorporated into proteins for tracking and imaging by use of fluorogenic tetrazines that become strongly fluorescent upon reaction. Selected notable examples of such applications are presented. The exceptional fast kinetics of this catalyst-free reaction, even using low concentrations of coupling partners, make it amenable for in vivo radiolabelling using pretargeting methodologies, which are also discussed. Finally, IEDDA reactions have recently found use in bioorthogonal decaging to activate proteins or drugs in gain-of-function strategies. We conclude by showing applications of the IEDDA reaction in the construction of biomaterials that are used for drug delivery and multimodal imaging, among others. The use and utility of the IEDDA reaction is interdisciplinary and promises to revolutionize chemical biology, radiochemistry and materials science.

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Section: Synthesis Of Tetrazine Derivativesmentioning

confidence: 99%

Inverse electron demand Diels–Alder reactions in chemical biology

2017

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“…Interestingly, the mechanism of the reaction was shown to not involve the formation of an N -chlorosulfonamide, despite previous reports suggesting NaOCl is a competent chlorinating agent for forming these species. − Subjecting an indole substrate to an independently prepared N -chlorosulfonamide under these reaction conditions gave none of the desired arene sulfonamidation product, but instead heteroarene aminochlorination with low efficiency, presumably via an electrophilic chlorination pathway. Instead, through steady-state SV studies, the authors show that NaOCl quenched the emission of the Ir(III) photocatalyst ( E 1/2 Ir(IV)/*Ir(III) = −0.96 V vs SCE in MeCN), forming an Ir(IV) species.…”

Section: N-centered Radical Generation From N–h Bonds Through Photoch...mentioning

confidence: 99%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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We present here a review of the photochemical and electrochemical applications of multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms in which both an electron and a proton are exchanged together, often in a concerted elementary step. As such, MS-PCET can function as a non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from a wide variety of common organic functional groups. We present an introduction to MS-PCET and a practitioner’s guide to reaction design, with an emphasis on the unique energetic and selectivity features that are characteristic of this reaction class. We then present chapters on oxidative N–H, O–H, S–H, and C–H bond homolysis methods, for the generation of the corresponding neutral radical species. Then, chapters for reductive PCET activations involving carbonyl, imine, other X=Y π-systems, and heteroarenes, where neutral ketyl, α-amino, and heteroarene-derived radicals can be generated. Finally, we present chapters on the applications of MS-PCET in asymmetric catalysis and in materials and device applications. Within each chapter, we subdivide by the functional group undergoing homolysis, and thereafter by the type of transformation being promoted. Methods published prior to the end of December 2020 are presented.

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“…We note that in this case the enzyme-catalyzed reaction is the rate-determining step. Other chemical − and electrochemical , methods for oxidation have also been applied for the in situ formation of Tz but not in combination with a one-pot click reaction. For example, 3,6-dichlorotetrazine was used as an organocatalyst in an aerobic oxidative-catalyzed nitroso-Diels–Alder reaction between arylhydroxylamines and dienecarbamates, but a detailed treatment thereof is outside the scope of this review …”

Section: Small Moleculesmentioning

confidence: 99%

Oxidation-Induced “One-Pot” Click Chemistry

et al. 2021

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Click chemistry has been established rapidly as one of the most valuable methods for the chemical transformation of complex molecules. Due to the rapid rates, clean conversions to the products, and compatibility of the reagents and reaction conditions even in complex settings, it has found applications in many molecule-oriented disciplines. From the vast landscape of click reactions, approaches have emerged in the past decade centered around oxidative processes to generate in situ highly reactive synthons from dormant functionalities. These approaches have led to some of the fastest click reactions know to date. Here, we review the various methods that can be used for such oxidation-induced “one-pot” click chemistry for the transformation of small molecules, materials, and biomolecules. A comprehensive overview is provided of oxidation conditions that induce a click reaction, and oxidation conditions are orthogonal to other click reactions so that sequential “click-oxidation-click” derivatization of molecules can be performed in one pot. Our review of the relevant literature shows that this strategy is emerging as a powerful approach for the preparation of high-performance materials and the generation of complex biomolecules. As such, we expect that oxidation-induced “one-pot” click chemistry will widen in scope substantially in the forthcoming years.

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Fluorous Analogue of Chloramine-T: Preparation, X-ray Structure Determination, and Use as an Oxidant for Radioiodination and s-Tetrazine Synthesis

Cited by 14 publications

References 70 publications

Inverse electron demand Diels–Alder reactions in chemical biology

Inverse electron demand Diels–Alder reactions in chemical biology

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Oxidation-Induced “One-Pot” Click Chemistry

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