Copper-free ‘click’: 1,3-dipolar cycloaddition of azides and arynes

Campbell-Verduyn, Lachlan S.; Elsinga, Philippus; Mirfeizi, Leila; Dierckx, Rudi; Feringa, Bernard

doi:10.1039/b812403e

Cited by 103 publications

(61 citation statements)

References 28 publications

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“…23 Consistent with computational predictions, 3-methoxybenzyne ( 1a ) and 3-fluorobenzyne ( 1b ) react with high regioselectivity (entries 1 and 2, respectively). A sequential decrease in regioselectivity was observed for reactions of arynes 1c – 1e , as the electron-withdrawing effects of the halide substituents decrease from F to Cl to Br to I (entries 3–5, respectively).…”

Section: Resultssupporting

confidence: 77%

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

et al. 2014

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The distortion/interaction model has been used to explain and predict reactivity in a variety of reactions where more common explanations, such as steric and electronic factors, do not suffice. This model has also provided new fundamental insight into regioselectivity trends in reactions of unsymmetrical arynes, which in turn, has fueled advances in aryne methodology and natural product synthesis. This article describes a systematic experimental and computational study of one particularly important class of arynes, 3-halobenzynes. 3-Halobenzynes are useful synthetic building blocks whose regioselectivities have been explained by several different models over the past few decades. Our efforts show that aryne distortion, rather than steric factors or charge distribution, are responsible for the regioselectivities observed in 3-haloaryne trapping experiments. We also demonstrate the synthetic utility of 3-halobenzynes for the efficient synthesis of functionalized heterocycles, using a tandem aryne trapping/cross-coupling sequence involving 3-chlorobenzyne.

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Section: Resultssupporting

confidence: 77%

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

et al. 2014

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“…[170] C 15 : colourless crystal (polyhedron), dimensions 0.15 × 0.14 × 0.06 mm Benzyl azide was synthesized according to a procedure reported in literature. [141,171] Benzyl bromide (98 %, 1.767 g benzyl bromide, 10.12 mmol) and sodium azide (0.987 g, 15.2 mmol) were dissolved in a mixture of acetone (40 ml) and water (10 ml). The reaction mixture was stirred for 20 hours at room temperature.…”

Section: -Ylidene]}-kckc'}dicopper(i) Bis(hexafluorophosphate)mentioning

confidence: 99%

Highly Active Dinuclear Copper Catalysts for Homogeneous Azide–Alkyne Cycloadditions

et al. 2012

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It is better to light a candle than to curse the dark. AbstractThe copper-catalyzed azide-alkyne cycloaddition for the synthesis of 1,4-disubstituted 1,2,3-triazoles (CuAAC) is a variant of Huisgen's 1,3-dipolar cycloaddition which disburdens the thermal reaction from its major drawbacks such as poor regioselectivity, long reaction times and harsh conditions. In contrast to the widely used "black box" reagent mixtures, a molecularly defined, highly active catalyst system for homogeneous CuAAC reactions has been developed in this PhD project. In dependence on the postulated stepwise mechanism, its most important structural feature is the presence of two copper(I) ions irreversibly bound in the same catalyst molecule.A highly modular and profitable synthesis for bistriazolium hexafluorophosphate salts as precursors for the ancillary ligand system was devised. In analogy to the CuAAC catalyst systems of general formula [(NHC) 2 Cu]PF 6 described in literature, novel dinuclear copper(I) complexes with a bistriazolylidene ligand backbone and 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr) as sacrificial ligand were prepared.However, these complexes did not show the expected high catalytic activity, most probably due to the strong coordination of the IPr ligands. In consequence, another family of dinuclear copper(I) complexes with m-coordinated acetate as labile ligand was synthesized by reaction of the bistriazolium hexafluorophosphate ligand precursors with copper(I) acetate in the presence of a base.The broad applicability and high catalytic activity of one of these bistriazolylidene dicopper acetate complexes was confirmed by a series of gaschromatographically mo-

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“…For HRMS measurements, ESI ionization was used. trans-2-Azidocyclohexanol and benzyl azide were prepared using literature procedures, from cyclohexene oxide [16] and benzyl bromide [17], respectively. AMTC (the catalytic ligand for copper-catalyzed azide-alkyne cycloaddition), was prepared according to a procedure developed by our group [15].…”

Section: Methodsmentioning

confidence: 99%

Fluorescent 1,2,3-triazole derivative of 3′-deoxy-3-azidothymidine: synthesis and absorption/emission spectra

Szafrański

Kasza²,

Kępczyński

et al. 2015

Heterocyclic Communications

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3′-Deoxy-3-azidothymidine (AZT, zidovudine) is a nucleoside-analog reverse transcriptase inhibitor, successfully used against the human immunodeficiency virus (HIV). Its structure contains an azide function, which makes it a useful substrate for 1,2,3-triazole synthesis, using the copper-catalyzed azide-alkyne cycloaddition, the flagship reaction of 'click chemistry'. Herein we present the synthesis and spectral characterization of its 1,2,3-triazole derivative containing a fluorenylmethyloxycarbonyl (fmoc) fluorescent fragment. The preparation and characteristics of a novel fluorescent probe, 9H-fluoren-9-ylmethyl prop-2-yn-1-yl carbonate (propargyl-fmoc) is also presented.

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Copper-free ‘click’: 1,3-dipolar cycloaddition of azides and arynes

Cited by 103 publications

References 28 publications

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

Highly Active Dinuclear Copper Catalysts for Homogeneous Azide–Alkyne Cycloadditions

Fluorescent 1,2,3-triazole derivative of 3′-deoxy-3-azidothymidine: synthesis and absorption/emission spectra

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