Direct Synthesis of 1,4‐Disubstituted‐5‐alumino‐1,2,3‐triazoles: Copper‐Catalyzed Cycloaddition of Organic Azides and Mixed Aluminum Acetylides

Zhou, Yuhan; Lecourt, Thomas; Micouin, Laurent

doi:10.1002/anie.200907016

Cited by 137 publications

(98 citation statements)

References 43 publications

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“…[2][3][4] Others [5][6][7] extended iClick to include the already prevalent [8][9] cycloaddition of an organic substrate to either a metal-azide or metal-acetylide. 7,[10][11][12][13][14][15][16][17][18][19][20][21] Important to this work, Gray et al 22 demonstrated that gold-acetylides and gold-azides will undergo cycloaddition to their organic counterparts. Despite the fact that several transition metals other than Cu(I) catalyze the azide-alkyne cycloaddition, including ruthenium, silver, and iridium, [23][24][25][26] it became apparent that not all metal-acetylide/azide species will participate in the iClick cycloaddition.…”

Section: Introductionmentioning

confidence: 99%

Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)

et al. 2015

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This report outlines the investigation of the iClick mechanism between gold(i)-azides and gold(i)-acetylides to yield digold triazolates. Isolation of digold triazolate complexes offer compelling support for the role of two copper(i) ions in CuAAC. In addition, a kinetic investigation reveals the reaction is first order in both Au(i)-N3 and Au(i)-C[triple bond, length as m-dash]C-R, thus second order overall. A Hammett plot with a ρ = 1.02(5) signifies electron-withdrawing groups accelerate the cycloaddition by facilitating the coordination of the second gold ion in a π-complex. Rate inhibition by the addition of free triphenylphosphine to the reaction indicates that ligand dissociation is a prerequisite for the reaction. The mechanistic conclusions mirror those proposed for the CuAAC reaction.

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Section: Introductionmentioning

confidence: 99%

Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)

et al. 2015

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“…Furthermore, recent advances in dipolar cycloadditions of 1-halo- and 1-metalloalkynes (formally internal alkynes) with organic azides have prompted additional investigation of the mechanism (19-22). In the case of 1-iodoalkynes, scission of the terminal alkyne-halogen bond to form a copper(I)-acetylide is not necessary for the cycloaddition to occur, suggesting that the copper catalyst effects the cycloaddition purely through weak π -interactions with the formally internal alkyne (Fig.…”

mentioning

confidence: 99%

Direct Evidence of a Dinuclear Copper Intermediate in Cu(I)-Catalyzed Azide-Alkyne Cycloadditions

Worrell

Malik

Fokin

2013

Science

713

556

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The copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) has become a commonly employed method for the synthesis of complex molecular architectures under challenging conditions. Despite the widespread use of copper-catalyzed cycloaddition reactions, the mechanism of these processes has remained difficult to establish due to the involvement of multiple equilibria between several reactive intermediates. Real-time monitoring of a representative cycloaddition process via heat flow reaction calorimetry revealed that monomeric copper acetylide complexes are not reactive toward organic azides unless an exogenous copper catalyst is added. Furthermore, crossover experiments with an isotopically enriched exogenous copper source illustrated the stepwise nature of the C–N bond-forming events and the equivalence of the two copper atoms within the cycloaddition steps.

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“…The direct regiospecific generation of halo-azoles would be an important advantage of this method, as these compounds are known pharmacophores, [16] as well as useful synthetic intermediates from which a variety of derivatives can be obtained by manipulation of the carbon-halogen bond. [17] In addition to the above-mentioned copper-catalyzed methods, which encompass 1-bromo and 1-iodoalkynes, [15,18] halotriazoles can be accessed by trapping reactive triazolyl intermediates, including 5-triazolyl-copper, [19] 5-aluminum, [20] 5-bismuth, [21] etc. or 4-triazolyl magnesium bromide [22] analogs with electrophilic halide reagents.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium‐Catalyzed Cycloadditions of 1‐Haloalkynes with Nitrile Oxides and Organic Azides: Synthesis of 4‐Haloisoxazoles and 5‐Halotriazoles

Oakdale

Sit

Fokin

2014

Chemistry A European J

108

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(Cyclopentadienyl)(cyclooctadiene) ruthenium(II) chloride [CpRuCl(cod)] catalyzes the reaction between nitrile oxides and electronically deficient 1-choro-, 1-bromo- and 1-iodoalkynes leading to 4-haloisoxazoles. Organic azides are also suitable 1,3-dipoles, resulting in 5-halo-1,2,3-triazoles. These air tolerant reactions can be performed at room temperature with 1.25 equiv of the respective 1,3-dipole relative to the alkyne component. Reactive 1-haloalkynes include propiolic amides, esters, ketones and phosphonates. Post-functionalization of the halogenated azole products can be accomplished using palladium-catalyzed cross-coupling reactions as well as via manipulation of reactive amide groups. The lack of catalysis observed with Cp*RuCl(cod) is attributed to steric demands of the Cp* (η5-C5Me5) ligand in comparison to the parent Cp (η5-C5H5). This hypothesis is supported by the poor reactivity of (η5-C5Me4CF3)RuCl(cod), which serves as a an isosteric mimic of Cp* and as an isoelectronic analog of Cp.

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Direct Synthesis of 1,4‐Disubstituted‐5‐alumino‐1,2,3‐triazoles: Copper‐Catalyzed Cycloaddition of Organic Azides and Mixed Aluminum Acetylides

Cited by 137 publications

References 43 publications

Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)

Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)

Direct Evidence of a Dinuclear Copper Intermediate in Cu(I)-Catalyzed Azide-Alkyne Cycloadditions

Ruthenium‐Catalyzed Cycloadditions of 1‐Haloalkynes with Nitrile Oxides and Organic Azides: Synthesis of 4‐Haloisoxazoles and 5‐Halotriazoles

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