1,3-Dipolar cycloaddition of [(o-carboran-1-yl)methyl]azide to alkynes

Ol’shevskaya, V. A.; Makarenkov, Anton V.; Kononova, Elena G.; Petrovskii, P. V.; Вербицкий, Е. В.; Rusinov, Gennady L.; Калинин, В. Н.; Charushin, Valery N.

doi:10.1134/s0012500810090090

Cited by 17 publications

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“…However, a high catalytic activity of copper(I) and copper(II) salts with more acceptor counter-ions, such as acetate, triflate and trifluoroacetatemonoanions, has been observed [32]; the catalytic activity of a series of copper(I) and copper(II) compounds in this reaction between the regular organic azides and acetylenes has been compared [33]. The obtained results suggest that copper(II) acetate is most active among them; we also found [18,31] that this cooper(II) salt efficiently catalyzes the cycloaddition reactions of ortho-carborane-(1)-methylazide with terminal acetylenes. In order to avoid formation of the complexes {Cu 2 (µ-C≡CR) 2 }, which are reported [33,34] to give the acetylene dimerization products in the presence of air oxygen, the "click" reactions under study were performed in an inert atmosphere (under argon).…”

Section: Resultsmentioning

confidence: 61%

“…The obtained monopropargylaminemacrobicyclic complexes underwent in this solvent the 1,3-dipolar cycloaddition reactions shown in Scheme 4 with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate. Earlier, we found [18,31] that copper(I)-based catalysts are insufficiently active for efficient performing of such 1,3-cycloaddition reactions with terminal acetylenes. Attempts using N-donor compounds such as bipyridine or ethylenediamine derivatives as the co-ligands allowing activation of copper(I) salts, in the case of ortho-carborane-(1)-methylazide as a dipolarophile component, caused formation of various by-products, the molecules of which contain a nido-carborane core.…”

Section: Resultsmentioning

confidence: 99%

“…The reagents used (FeCl 2 • 4H 2 O, propargylamine, triethylamine, morpholine, diethylamine and copper acetate(II), sorbents and organic solvents were obtained commercially (SAF); ortho-carborane-1-methylazide, the dichloroclathrochelate precursor 9 and its dipropargylamine derivative 16 were prepared as described elsewhere [18,31,35,36].…”

Section: General Informationmentioning

confidence: 99%

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Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents—The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s)

et al. 2021

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A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their “click” 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28º. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C–H…H–B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C–H…F–B interaction with an adjacent carboranoclathrochelate molecule. The N–H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1Н-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal.

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Section: Resultsmentioning

confidence: 61%

Section: Resultsmentioning

confidence: 99%

Section: General Informationmentioning

confidence: 99%

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Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents—The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s)

et al. 2021

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“…4 There are three main approaches to the synthesis of o-aminoalkyl carboranes 1-NH 2 (CH 2 ) n -1,2-C 2 B 10 H 11 . The first one is based on the reaction of decaborane (14) with protected o-aminoalkylacetylenes followed by removal of protecting groups. [5][6][7][8] A similar approach includes alkylation of ortho-carborane with protected o-halogenalkylamines.…”

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confidence: 99%

“…5,12 This synthetic scheme requires more steps, however, it is more universal and can be used for synthesis of o-carboranylalkyl azides as well. 7,13,14 The same approach can be used for introduction of the amino group into related carborane systems. [15][16][17] A common problem in carborane chemistry is synthesis of their monosubstituted derivatives.…”

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confidence: 99%