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Synthesis of 1,2,3-triazoles and benzotriazoles

Recent Literature

A Pd-catalyzed synthesis of 1H-triazoles from alkenyl halides and sodium azide represents a completely new reactivity pattern in the context of Pd chemistry.
J. Barluenga, C. Valdés, G. Beltrán, M. Escribano, F. Aznar, Angew. Chem. Int. Ed., 2006, 45, 6893-6896.

J. Barluenga, C. Valdés, G. Beltrán, M. Escribano, F. Aznar, Angew. Chem. Int. Ed., 2006, 45, 6893-6896.

Tris(2-benzimidazolylmethyl)amines are superior accelerating ligands for the copper(I)-catalyzed azide-alkyne cycloaddition reaction. The water-soluble ligand (BimC₄A)₃ was found to be especially convenient for the rapid and high-yielding synthesis of several functionalized triazoles with 0.01-0.5 mol % Cu.
V. O. Rodionov, S. I. Presolski, S. Gardinier, Y.-H. Lim, M. G. Finn, J. Am. Chem. Soc., 2007, 129, 12696-12704.

Immobilized copper nanoparticles in aluminum oxyhydoxide fiber showed high catalytic activity for the cycloaddition of various alkynes to azides at room temperature. The catalyst can be recycled up to five times without significant loss of activity.
I. S. Park, M. S. Kwon, Y. Kim, J. S. Lee, J. Park, Org. Lett., 2008, 10, 497-500.

Highly efficient click chemistry between azides and terminal alkynes can be heterogeneously catalyzed by copper nanoparticles mounted within the pores of activated charcoal. Reactions can be accelerated with stoichiometric Et₃N or by increasing the reaction temperature using microwave irradiation.
B. H. Lipshutz, B. R. Taft, Angew. Chem. Int. Ed., 2006, 45, 8235-8238.

The CuI-catalyzed, stepwise cycloaddition of azides to terminal alkynes exhibits broad scope and provides 1,4-disubstituted 1,2,3-triazoles in excellent yields and high regioselectivity.
V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. Int. Ed., 2002, 41, 2596-2599.

Copper(I) immobilized on 3-aminopropyl-functionalized silica gel catalyzed the reaction of terminal alkynes with benzyl- or alkyl halides and sodium azide in ethanol to give 1,4-disubstituted 1,2,3-triazoles in good to excellent yields. This procedure allows the conversion of unstable low-molecular-weight azides. Furthermore, the silica-supported copper could be recovered and recycled by simple filtration.
T. Miaoa, L. Wang, Synthesis, 2008, 363-368.

A copper(I)-catalyzed three-component reaction of amines, propargyl halides and azides forms 1-substituted-1H-1,2,3-triazol-4-ylmethyl)-dialkylamines in water. Synthetic advantages are high atom economy, low environmental impact, atmospheric oxygen, wide substrate scope, mild reaction condition and good yields.
Z.-Y. Yan, Y.-B. Zhao, M.-J. Fan, W.-M. Liu, Y.-M. Liang, Tetrahedron, 2005, 61, 9331-9337.

A method for the regiospecific synthesis of 1,4,5-trisubstituted-1,2,3-triazole catalyzed by copper(I) iodide was developed. This is the first example of a regiospecific synthesis of 5-iodo-1,4-disubstituted-1,2,3-triazole, which can be further elaborated to a range of 1,4,5-trisubstituted-1,2,3-triazole derivatives.
Y.-M. Wu, J. Deng, Y. L. Li, Q.-Y. Chen, Synthesis, 2005, 1314-1318.

A reliable and operationally simple one-pot reaction for a one-carbon homologation of various aldehydes followed by Cu-catalyzed azide-alkyne click chemistry gives 1,4-disubstituted 1,2,3-triazoles in good yields without the need for isolation of the alkyne intermediates.
D. Luvino, C. Amalric, M. Smietana, J.-J. Vasseur, Synlett, 2007, 3037-3041.

1,2,3-Triazoles were prepared in good to modest yields by cycloaddition of alkyl azides onto enol ethers under solventless conditions. The reaction can access ring-fused triazoles that are unavailable by azide-alkyne cycloadditions and is easily scalable. The 1,2,3-triazole products bear functionality that may be readily derivatized.
D. R. Rogue, J. L. Neill, J. W. Antoon, E. P. Stevens, Synthesis, 2005, 2497-2502.

The synthesis of aromatic azides from the corresponding amines is accomplished under mild conditions with tert-butyl nitrite and azidotrimethylsilane. 1,4-Disubstituted 1,2,3-triazoles were obtained in excellent yields from various aromatic amines without the need for isolation of the azide intermediates.
K. Barral, A. D. Moorhouse, J. E. Moses, Org. Lett., 2007, 9, 1809-1811.

Triazoles have been synthesized via a three-component coupling reaction of unactivated terminal alkynes, allyl carbonate, and trimethylsiyl azide under Pd(0)-Cu(I) bimetallic catalysis. The deallylation of the resulting allyltriazoles is described.
S. Kamijo, T. Jin, Z. Huo, Y. Yamamoto, J. Am. Chem. Soc., 2003, 125, 7786-7787.

TBAF-catalyzed [3 + 2] cycloadditions of 2-aryl-1-cyano- or 2-aryl-1-carbethoxy-1-nitroethenes with TMSN₃ under solvent free conditions allow the preparation of 4-aryl-5-cyano- or 4-aryl-5-carbethoxy-1H-1,2,3-triazoles under mild reaction conditions with good to excellent yields.
D. Amantini, F. Fringuelli, O. Piermatti, F. Pizzo, E. Zunino, L. Vaccaro, J. Org. Chem., 2005, 70, 6526-6529.

D. Amantini, F. Fringuelli, O. Piermatti, F. Pizzo, E. Zunino, L. Vaccaro, J. Org. Chem., 2005, 70, 6526-6529.

Triazole-based monophosphine ligands have been prepared via efficient cycloadditions. Palladium complexes derived from these ligands are highly active catalysts for Suzuki-Miyaura coupling and amination reactions of aryl chlorides.
D. Liu, W. Gao, Q. Dai, X. Zhang, Org. Lett., 2005, 7, 4907-4910.

A highly efficient method for the synthesis of multisubstituted 1,2,3-triazoles via a direct Pd-catalyzed C-5 arylation has been developed.
S. Chuprakov, N. Chernyak, A. S. Dudnik, V. Gevorgyan, Org. Lett., 2007, 9, 2333-2336.

The formation of 1,5-disubstituted 1,2,3-triazoles from aryl azides and alkynes was readily accomplished using [Cp*RuCl]₄ as catalyst in dimethylformamide. The reaction provided higher yields, cleaner product, and shorter reaction times when carried out under microwave irradiation.
L. K. Rasmussen, B. C. Boren, V. V. Fokin, Org. Lett., 2007, 9, 5337-5339.

A [3 + 2] cycloaddition of azides to benzynes affords a rapid and easy entry to a variety of substituted, functionalized benzotriazoles under mild conditions.
F. Shi, J. P. Waldo, Y. Chen, R. C. Larock, Org. Lett., 2008, 10, 2409-2412.