1.3‐Dipolare Cycloadditionen, XXV. Der Nachweis des freien Diphenylnitrilimins als Zwischenstufe bei Cycloadditionen

Clovis, James S.; Eckell, Albrecht; Huisgen, Rolf; Sustmann, Reiner

doi:10.1002/cber.19671000108

Cited by 201 publications

(120 citation statements)

References 13 publications

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“…One such tool is the photoinduced click reactions that hold a great promise to bring the spatial and temporal precision associated with light to the study of biomolecular systems in living systems [2]. Inspired by the seminal work of Rolf Huisgen on the 1,3-dipolar cycloaddition reaction of the diphenyltetrazole as a photoactivatable 1,3-dipole precursor [3], we reported in 2008 that the high reactivity of the diphenyltetrazole can be harnessed for protein labeling both in aqueous medium [4••] and inside bacterial cells [5••], owing to the fact that the pyrazoline cycloadducts are fluorescent. We termed this tetrazole-alkene cycloaddition reaction “photoclick chemistry” because of the necessity of photon in initiating the reaction and the satisfaction of the criteria for a “spring-loaded” click reaction proposed by Sharpless [6].…”

Section: Introductionmentioning

confidence: 99%

Photoclick chemistry: a fluorogenic light-triggered in vivo ligation reaction

Ramil

Lin

2014

Current Opinion in Chemical Biology

122

100

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The ability to use chemical reactivity to monitor and control biomolecular processes with a spatial and temporal precision motivated the development of light-triggered in vivo chemistries. To this end, the photoinduced tetrazole-alkene cycloaddition, also termed “photoclick chemistry” offers a very rapid chemical ligation platform for the manipulation of biomolecules and matrices in vivo. Here we outline the recent developments in the optimization of this chemistry, ranging from the search for substrates that offer two-photon photoactivatability, superior reaction kinetics, and/or genetic encodability, to the study of the reaction mechanism. The applications of the photoclick chemistry in protein labeling in vitro and in vivo as well as in preparing “smart” hydrogels for 3D cell culture are highlighted.

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Section: Introductionmentioning

confidence: 99%

Photoclick chemistry: a fluorogenic light-triggered in vivo ligation reaction

Ramil

Lin

2014

Current Opinion in Chemical Biology

122

100

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“…[11] A concerted reaction mechanism was proposed, whereby the diaryl tetrazole undergoes a facile cycloreversion reaction upon photoirradiation to release N 2 and generate in situ a nitrile imine dipole, which cyclizes spontaneously with an alkene dipolarophile to afford a pyrazoline cycloadduct (Scheme 1). The photolysis of diaryl tetrazoles was found to be extremely efficient upon UV irradiation at 290 nm, with quantum yields in the range 0.5-0.9.…”

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confidence: 99%

A Photoinducible 1,3‐Dipolar Cycloaddition Reaction for Rapid, Selective Modification of Tetrazole‐Containing Proteins

et al. 2008

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Bioorthogonal chemistry provides an exciting new strategy to visualize protein expression, track protein localization, measure protein activity, and identify protein interaction partners in living systems.[1] Two steps are typically involved in this approach: 1) the incorporation of a bioorthogonal group into a protein through either a biochemical pathway or semisynthesis; 2) a site-specific reaction between the protein that carries the bioorthogonal group and a cognate small-molecule probe. Although a plethora of methods have been developed to address the first step, such as non-sense suppression mutagenesis, [2] expressed protein ligation, [3] metabolic engineering, [4] and tagging-via-substrate, [5] only a small number of bioorthogonal reactions are known for the second step. These site-specific reactions include the acid-catalyzed nucleophilic addition of hydrazine to a ketone or aldehyde, [6] Staudinger ligation, [7] Cu I -catalyzed azide-alkyne 1,3-dipolar cycloaddition (click chemistry), [8] strain-promoted azide-alkyne 1,3-dipolar cycloaddition, [9] and the oxidative coupling of aniline.[10] To fully realize the potential of bioorthogonal chemistry in probing protein function, there is an urgent need for the discovery of additional bioorthogonal reactions with robust reaction attributes. Herein, we report a bioorthogonal, photoinducible 1,3-dipolar cycloaddition reaction that allows rapid and highly selective modification of proteins carrying a diaryl tetrazole group in biological media.Forty years ago, Huisgen and co-workers reported a photoactivated 1,3-dipolar cycloaddition reaction between 2,5-diphenyltetrazole and methyl crotonate.[11] A concerted reaction mechanism was proposed, whereby the diaryl tetrazole undergoes a facile cycloreversion reaction upon photoirradiation to release N 2 and generate in situ a nitrile imine dipole, which cyclizes spontaneously with an alkene dipolarophile to afford a pyrazoline cycloadduct (Scheme 1). The photolysis of diaryl tetrazoles was found to be extremely efficient upon UV irradiation at 290 nm, with quantum yields in the range 0.5-0.9.[12] Despite its robust mechanism, this photoactivated reaction has seen very few applications in the past four decades.[13]In our initial studies, we identified an extremely mild photoactivation procedure in the use of a hand-held UV lamp from UVP (UVM-57, 302 nm, 115 V, 0.16 amps). Under these mild conditions, the solvent compatibility, functional-group tolerance, regioselectivity, and yield of the photoactivated 1,3-dipolar cycloaddition reaction were excellent. [14] We then examined the reaction kinetics by incubating a tetrazole peptide with acrylamide in phosphate-buffered saline (PBS) at pH 7.5 under UV light (302 nm; see Figure S1 in the Supporting Information). We found that the photolysis of the tetrazole peptide to generate the nitrile imine intermediate was extremely rapid, with a first-order rate constant k 1 = 0.14 s À1 ; the subsequent cycloaddition with the dipolarophile acrylamide proceeded very efficiently, w...

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“…[5] Under UV light, decarbonylation occurs, releasing strained alkynes reacting rapidly with azides in solution and producing fluorophore patterns. Following the inspiring work of Lin and co-workers, [6] who resurrected the seminal work of Huisgen and Sustmann, [7] we recently explored the photogeneration of nitrile imines from immobilized diaryl tetrazoles to pattern different polymers on cellulose by 1,3-dipolar cycloaddition with maleimide-functionalized macromolecules.…”

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confidence: 99%