Strain-promoted double-click reaction for chemical modification of azido-biomolecules

Kii, Isao; Shiraishi, Akira; Hiramatsu, Toshiyuki; Matsushita, Tomonori; Uekusa, Hidehiro; Yoshida, Suguru; Yamamoto, Makoto; Kudo, Akira; Hagiwara, Masatoshi; Hosoya, Takamitsu

doi:10.1039/c0ob00003e

Cited by 103 publications

(104 citation statements)

References 40 publications

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“…Incubation with 10 led to efficient labelling in only 2 h, while only minor labelling was observed upon similar incubation with bis-azido-triethylene glycol reagent 11. In this respect, the here presented one-pot sequential SPAAC for labelling of a BCN-bearing protein bears resemblance, yet is nicely complementary, to the procedure reported by Hosoya et al 16 for three-component labelling of an azido-bearing protein in the presence of Sondheimer diyne and an azido-fluorophore.…”

Section: Resultsmentioning

confidence: 89%

“…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 . In general it may be concluded that, despite tremendous synthetic effort, optimization of cycloaddition of azides with (stable) cyclooctynes has, depending on specific conditions, leveled off around 0.2-0.5 M À 1 s À 1 (refs 1,4).…”

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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: Resultsmentioning

confidence: 89%

mentioning

confidence: 99%

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

Rooijen²,

et al. 2014

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“…As a part of our studies focusing on highly strained alkynes, including arynes [24][25][26][27][28][29][30][31][32][33][34], we have been working on a project to develop new aryne generation methods. For example, we have recently succeeded in efficiently generating arynes from ortho-iodoaryl triflates bearing sensitive functional groups using a trimethylsilylmethyl Grignard reagent as an activator [30,31,33] instead of conventional activators such as n-butyllithium [35] or a turbo-Grignard reagent [36].…”

Section: Open Accessmentioning

confidence: 99%

An Alternative Method for Generating Arynes from ortho-Silylaryl Triflates: Activation by Cesium Carbonate in the Presence of a Crown Ether

et al. 2015

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“…1 The azido group is small, stable in biological systems, and selectively reactive with phosphines such as 1 via Staudinger ligation 2 and with cyclooctynes (e.g. 2-5) via Huisgen [3+2] cycloaddition [3][4][5][6][7][8][9][10][11] (Figure 1). …”

Section: Introductionmentioning

confidence: 99%

Development and evaluation of new cyclooctynes for cell surface glycan imaging in cancer cells

et al. 2011

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Two reagents have been synthesized for selective labeling of cell surface azidoglycans, an unusually stable version of a dibenzocyclooctyne (TMDIBO) and a third-generation difluorinated cyclooctyne (DIFO3). Both syntheses are efficient with minimal purification, and the dibenzocyclooctyne is stable under basic and acidic conditions. Flow cytometric measurements with azidosugar labeled cancer cells, in which these reagents were linked to the fluorophore Alexa Fluor 647, gave a signal-to-background ratio of up to 35 with TMDIBO as compared to ≈10 for DIFO3 and ≈5 for a phosphine reagent. TMDIBO-based probes should have applications in molecular imaging of cell surface glycans in vivo.

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Strain-promoted double-click reaction for chemical modification of azido-biomolecules

Abstract: The strain-promoted "double-click" (SPDC) reaction using Sondheimer diyne, a novel convergent method conjugating three molecules spontaneously, has enabled us to readily modify an azido-biomolecule with a small reporter azido-molecule.

Cited by 103 publications

References 40 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

An Alternative Method for Generating Arynes from ortho-Silylaryl Triflates: Activation by Cesium Carbonate in the Presence of a Crown Ether

Development and evaluation of new cyclooctynes for cell surface glycan imaging in cancer cells

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