Readily Accessible Bicyclononynes for Bioorthogonal Labeling and Three‐Dimensional Imaging of Living Cells

Dommerholt, Jan; Schmidt, Samuel; Temming, Rinske P.; Hendriks, Linda; Rutjes, Floris P. J. T.; Hest, Jan C. M. van; Lefeber, Dirk; Friedl, Peter; Delft, Floris L. van

doi:10.1002/anie.201003761

Cited by 640 publications

(610 citation statements)

References 37 publications

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“…Not surprisingly, near-identical rate constants were determined for azides A-C in reaction with BCN alcohol (6a) or with a DIBAC derivative (3a). Similar to earlier reported data 10,15 , an approximately three-to fourfold higher reactivity was observed for DIBAC versus BCN (k BCN :k DIBAC ). It must be noted, however, that the absolute rate constants as measured by this protocol are about twofold lower than those reported earlier in other solvent systems 1 .…”

Section: Resultssupporting

confidence: 90%

“…Our investigations on the structure-reactivity relationship of azides in strain-promoted cycloadditions were stimulated by the fact that much effort has been devoted to the development of more reactive cyclooctynes 8,[10][11][12][13][14][15] , but only scant information is available on the influence of the azide structure on SPAAC rates 19,20 . In addition, it struck us that SPAAC reaction rate constants are nearly always determined with an aliphatic azide (typically benzyl azide), but rarely with an aromatic azide.…”

Section: Resultsmentioning

confidence: 99%

“…Yet more reactive probes such as biarylazacyclooctynones (BARAC) 13 (4) and tetramethylthiacycloheptyne (TMTH) 14 (5) exist, but suffer from poor stability. Bicyclo[6.1.0]non-4yne (BCN, 6) is a stable, non-benzoannulated cyclooctyne that is synthetically readily accessible 15 , but generally regarded to be less reactive than DIBAC. Finally, Sondheimer diyne (7) is unique in the sense that it is able to react sequentially with two azides with distinctly different reaction rates 16 .…”

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confidence: 99%

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Highly accelerated inverse electron-demand cycloaddition of electron-deficient azides with aliphatic cyclooctynes

Rooijen²,

et al. 2014

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Strain-promoted azide-alkyne cycloaddition (SPAAC) as a conjugation tool has found broad application in material sciences, chemical biology and even in vivo use. However, despite tremendous effort, SPAAC remains fairly slow (0.2-0.5 M À 1 s À 1 ) and efforts to increase reaction rates by tailoring of cyclooctyne structure have suffered from a poor trade-off between cyclooctyne reactivity and stability. We here wish to report tremendous acceleration of strain-promoted cycloaddition of an aliphatic cyclooctyne (bicyclo[6.1.0]non-4-yne, BCN) with electron-deficient aryl azides, with reaction rate constants reaching 2.0-2.9 M À 1 s À 1 . A remarkable difference in rate constants of aliphatic cyclooctynes versus benzoannulated cyclooctynes is noted, enabling a next level of orthogonality by a judicious choice of azidecyclooctyne combinations, which is inter alia applied in one-pot three-component protein labelling. The pivotal role of azide electronegativity is explained by density-functional theory calculations and electronic-structure analyses, which indicates an inverse electron-demand mechanism is operative with an aliphatic cyclooctyne.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Highly accelerated inverse electron-demand cycloaddition of electron-deficient azides with aliphatic cyclooctynes

Rooijen²,

et al. 2014

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“…In a particularly striking example, Laughlin et al 94 utilized DIFOs to visualize the development of glycans during zebrafish embryo growth, demonstrating a high degree of specificity and 'bio-orthogonality' at slightly faster rates than previously reported using the Staudinger ligation. Further enhancements in rates have been reported through the generation of biarylazacyclooctynones 95 and cyclopropyl-fused bicyclononynes 96 (Fig. 4a).…”

Section: Review Nature Communications | Doi: 101038/ncomms5740mentioning

confidence: 72%

“…4b). Inspired by the work of Dommerholt et al 96 , it was found that trans-bicyclononene reacted at yet faster rates (while noting the caveats on rate determinations given above) 103 . In addition to allowing labelling of highly dynamic processes, such rapid and efficient reactions allow the concentrations of reactive partners to be lowered significantly, reducing background labelling particularly in cases where it is REVIEW implausible to wash away excess reagent, such as intracellularly or in animal models 104 .…”

Section: Review Nature Communications | Doi: 101038/ncomms5740mentioning

confidence: 99%

Selective chemical protein modification

2014

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Click Reactions: Azide‐Alkyne Cycloaddition

Jung¹,

Bräse²

2013

Kirk-Othmer Encyclopedia of Chemical Technology

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The term “Click‐chemistry” is a general concept that describes reactions of enormous interest because of their unique characteristics for the synthetic chemistry. Many typical Click‐reactions –among them the Diels Alder reaction and 1,3‐dipolar cycloaddition reactions– have been known for a long time. The most famous amongst them is the copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) which opens up outstanding opportunities in various fields of science and technology. Since the development of the CuAAC by Meldal and Sharpless it gained enormous attention not only in the field of chemistry, but also in biology and materials sciences. In parallel to the development of new applications of the CuAAC, the need for further adaption of the original Click‐procedure e.g. for bioorthogonal approaches got obvious. Nowadays, the broader scope of the CuAAC‐reaction is often paid for with the abandoning of at least one of the mandatory Click requirements and the modified procedures do not stand the general criteria any more. This review will give an overview of the current progress of the famous CuAAC‐(Click)‐reaction, including postulated mechanisms and importance of additives. It will sum up the challenges that have been mastered under critical consideration of the fulfillment of the original Click‐criteria.

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Readily Accessible Bicyclononynes for Bioorthogonal Labeling and Three‐Dimensional Imaging of Living Cells

Cited by 640 publications

References 37 publications

Highly accelerated inverse electron-demand cycloaddition of electron-deficient azides with aliphatic cyclooctynes

Highly accelerated inverse electron-demand cycloaddition of electron-deficient azides with aliphatic cyclooctynes

Selective chemical protein modification

Click Reactions: Azide‐Alkyne Cycloaddition

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