β-Cyclodextrin-catalyzed three-component synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles from propynals, trimethylsilyl azide and malononitrile in water

doi:10.1016/j.mencom.2016.07.020

Mendeleev Communications

Volume 26, Issue 4, July–August 2016, Pages 326-328

https://doi.org/10.1016/j.mencom.2016.07.020 Get rights and content

An efficient green method for the selective synthesis of new 4,5-disubstituted 1H-1,2,3-triazoloalkylidenes via the β-cyclodextrin-catalyzed three-component reaction between substituted propynals, trimethylsilyl azide and malononitrile in water at room temperature has been developed.

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References (24)

G. Aromí et al.
Coord. Chem. Rev.
(2011)
H. Duan et al.
J. Am. Chem. Soc.
(2009)
B. Schulze et al.
Chem. Soc. Rev.
(2014)
J.C. Jewett et al.
Chem. Rev.
(2010)
L.M. Gaetke et al.
Toxicology
(2003)
A.S. Medvedeva et al.
Chem. Heterocycl. Compd. (Engl. Transl.)
(2014)
A.S. Medvedeva et al.
Russ. J. Org. Chem.
(2010)
P.D. Jarowski et al.
Org. Lett.
(2008)
S.G. Agalave et al.
Chem. Asian J.
(2011)
G.C. Tron et al.
Med. Res. Rev.
(2008)
V.P. Krivopalov et al.
Russ. Chem. Rev.
(2005)
V. Bakulev et al.
M. Ichikawa et al.
J. Mater. Chem.
(2011)
A. Qin et al.
Chem. Soc. Rev.
(2010)
N. Gimeno et al.
J. Mater. Chem.
(2012)
L.L. Fershtat et al.
Mendeleev Commun.
(2015)
D.S. Kopchuk et al.
Mendeleev Commun.
(2015)
V.V. Rostovtsev et al.
Angew. Chem. Int. Ed.
(2002)
C.W. Tornøe et al.
J. Org. Chem.
(2002)

C.W. Tornøe et al.

Chem. Rev.

(2008)

J.M. Holub et al.

Chem. Soc. Rev.

(2010)

K. Dabak et al.

Eur. J. Med. Chem.

(2003)

P.W. Baures

Org. Lett.

(1999)

S. Komeda et al.

J. Am. Chem. Soc.

(2002)

T. Harrison et al.

J. Med. Chem.

(2001)

T. Weide et al.

ACS Med. Chem. Lett.

(2010)

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As an excellent bioorthogonal reaction, CuAAC reaction has been widely used in biological research. In this work, three cyclodextrin derivatives β-CD-3, β-CD-4 and CD-P were synthesized in different ways. Among them, use of trace amounts of the β-CD-3 could efficiently promote the CuAAC reaction under mild conditions. Only using 20 ppm concentration of β-CD-3-Cu(I), the TON of the reaction was up to 45,000, and the catalyst still has high catalytic activity after repeated cycling, which may be attributed to its chelating structure formed by coordination with copper more stable than β-CD-4-Cu(I) and CD-P-Cu(I). In addition, we have also proved that the construction of supramolecular catalytic systems can effectively achieve extracellular click reactions at ultra-low concentrations, and therefore can be applied to the synthesis of various functional compounds such as catalysis, imaging, targeting and medicine.
Organosilicon azoles: Structure, silylotropy and NMR spectroscopy
2021, Advances in Heterocyclic Chemistry
Citation Excerpt :
The results of our studies of various azole derivatives are published in monographs [2003DISS, 2009MI2] and several reviews dedicated to tautomerism of azoles [2018AHC(124)233], the chemistry of five-membered nitroazoles [1994RHC27, 1994ROC1141], and their benzanalogs [2006THS321, 2005THS327], the chemistry of silicon-containing azoles [2001ROC149], Nuclear magnetic resonance (NMR) spectroscopy and mass-spectrometry of nitroazoles [1996MI1, 1998THS443], and electronic effects of five-membered nitrogen-containing aromatic heterocycles [1986RCR411]. Our on-going research is devoted to the chemistry, structure, and application of organosilicon azoles and related silicon-containing materials [1998JOMC129, 1998RCB1418, 2001ROC1891, 2002ROC344, 2003ROC1393, 2003ROC1522, 2004ROC1804, 2006RGC1023, 2007MRC661, 2007RGC2145, 2010ROC1675, 2011JOMC1964, 2011ROC298, 2014CHE967, 2014CHE1332, 2014ROC1377, 2015CHE381, 2015MC34, 2015MCP227, 2015MI1, 2015RCB2261, 2015RGC2304, 2016MC326, 2016MC426, 2016RCB1081, 2016ROC1229, 2017MC175, 2017MC352, 2017RCB2253, 2017ROC413, 2017ROC1066, 2017ROC1510, 2018MI1, 2019DP336, 2019ROC352]. The synthesis and structure of siloxane derivatives of azoles (1,2,4-triazoles, benzimidazoles, benzotriazoles, benzothiazole), [2014CHE1332, 2014ROC1377, 2015RCB2261, 2017MC352], acetylenic silylderivatives of benzimidazole [2015RGC2304], organosilicon cyclophanes of benzimidazole and benzotriazole [2016MC426], silanes and siloxanes of imidazoles [2017ROC413, 2017ROC1066], silicon-containing derivatives of 1,2,3-triazoles, oxazoles, isoxazoles and imidazoles [2003ROC1507, 2015OL1826, 2017MC175, 2017RCB2253, 2017T3979], organosilicon macroheterocycles [2017RCB2339] have been studied.
The present review summarizes comprehensive data (from the author's work and the literature) on structure and silylotropy rearrangements of organosilicon azoles (pyrazoles, imidazoles, thiazoles, 1,2,3- and 1,2,4-triazoles, tetrazoles and benzazoles) and related compounds by multinuclear ¹H, ¹³C, ¹⁵N and ²⁹Si NMR spectroscopy. Special emphasis is given to studies of silylated azoles by dynamic NMR spectroscopy. The structure of C- and N-trimethylsilyl derivatives of azoles, their bistrimethylsilyl analogs, and bicyclic organosilicon derivatives of azoles are discussed. The influence of the nature of the heterocycle and substituent on the equilibrium constants and the values of free activation energy of silylotropic transformations are analyzed. The catalytic effect of halogens and trimethylhalogensilanes on the silylotropy processes in N-trimethylsilylazoles is covered in detail. Critical analysis of literature data on structure of silicon-containing azoles is presented.
Tautomerism and Structure of Azoles: Nuclear Magnetic Resonance Spectroscopy
2018, Advances in Heterocyclic Chemistry
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Tautomerism and isomerism of 1,2,3-triazoloiminodiazomethane in the gas phase have been studied by means of ab initio calculations at the HF/6-31G** level [2000H291]. Diastereomerism and tautomerism of 4,5-dihydro-1H-1,2,3-triazoles [2002JCS(P2)126], structure of 1H-1,2,3-triazole-5-carbaldehydes and related compounds [2004ROC1804, 2014CHE967, 2016MC326], 2-substituted-1,2,3-triazoles [2008OL3171, 2010CHE79], 1,4-disubstituted-1,2,3-triazoles [2012S3353, 2015SL187, 2015S199], alkylated products of 4(5)-nitro-1,2,3-triazole [2013RCB111], a novel class of selective inhibitors of matrix metalloproteinase-2 on the base of 4-aryl-1,2,3-triazoles [2013CHE1108], and also structure of other triazoles [2015CP294, 2016CHE1078] have been investigated by NMR spectroscopy. The possibility of chlorotropy in 1,2,3-triazoles and benzotriazoles has been considered [1985H2225] since it has been reported that chlorine exchange was taking place in 1-chloro-4,5-diphenyl-1,2,3-triazole [1979JCS(CC)419].
This review provides comprehensive data (from the author's work and the literature) on tautomerism of pyrazoles, imidazoles, 1,2,3- and 1,2,4-triazoles, tetrazoles, benzimidazoles, benzimidazolones, benzotriazoles, and related compounds by multinuclear ¹H, ¹³C, ¹⁵N nuclear magnetic resonance (NMR) spectroscopy. Emphasis is given to studies of azoles by multinuclear dynamic NMR spectroscopy because prototropic transformations of almost all azoles in solution proceed so quickly. Quantum-chemical investigations of tautomeric azoles are covered in detail. Critical analysis of literature data on the tautomerism of azoles is presented. Theoretical studies of structure and reactivity of azoles are most intriguing because correct interpretation of their chemical behavior and biological activity depends on an understanding the factors determining relative stability of their tautomers. ¹⁵N NMR spectroscopy is the most reliable and fast technique for structural and tautomeric determination of nitrogen-containing heteroaromatic compounds.
Synthesis of 5-aminoisoxazoles from 3-trimethylsilylprop-2-ynamides
2017, Mendeleev Communications
Microwave assisted solvent- and catalyst-free three-component synthesis of NH-1,2,3-triazoloimines
2017, Tetrahedron
Highly efficient microwave-assisted solvent- and catalyst-free multicomponent synthesis of 5-R-imino-[4-trialkylsilyl(germyl)]-1H-1,2,3-triazoles from Si/Ge-substituted propynals, trimethylsilyl azide and functionalized primary amines has been developed. In the case of 2-aminoethanethiol, 4-element substituted 5-(1,3-thiazolan-2-yl)-1H-1,2,3-triazoles have been obtained. Their heterolysis by MeOH at room temperature leads to the corresponding triazoloimines in high yield.
Catalyst-free three-component synthesis of hydroxyalkyltriazolylmethylidene barbiturates
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β-Cyclodextrin-catalyzed three-component synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles from propynals, trimethylsilyl azide and malononitrile in water

Graphical abstract

Coord. Chem. Rev.

J. Am. Chem. Soc.

Chem. Soc. Rev.

Chem. Rev.

Toxicology

Chem. Heterocycl. Compd. (Engl. Transl.)

Russ. J. Org. Chem.

Org. Lett.

Chem. Asian J.

Med. Res. Rev.

Russ. Chem. Rev.

J. Mater. Chem.

Chem. Soc. Rev.

J. Mater. Chem.

Mendeleev Commun.

Mendeleev Commun.

Angew. Chem. Int. Ed.

J. Org. Chem.

Chem. Rev.

Chem. Soc. Rev.

Eur. J. Med. Chem.

Org. Lett.

J. Am. Chem. Soc.

J. Med. Chem.

ACS Med. Chem. Lett.