Synthesis of podands with nido-carboranyl groups as a basis for construction of crown ethers with an incorporated metallacarborane moiety

Stogniy, Marina Yu.; Kazakov, Grigoriy S.; Sivaev, Igor B.; Bregadze, V. I.

doi:10.1007/s11172-013-0095-0

Cited by 13 publications

(5 citation statements)

References 42 publications

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“…The first stage of its manufacture includes N-methylation of 3-methyl-6-nitro-1H-indazole. This process is critical stage since desirable 2,3-dimethyl-6-nitro-2H-indazole (5) is always contaminated with isomeric 1,3-dimethyl-6-nitro-1H-indazole (6). Several papers have reported optional reagents and conditions for preparation of 5 [37][38][39], however, laborious recrystallizations have been still required to purify 5 from isomeric 6.…”

Section: Resultsmentioning

confidence: 99%

“…Cyclic oxonium derivatives of polyhedral boron hydrides are well studied due to their use as convenient starting compounds for the preparation of various functional derivatives [1,2]. In particular, this approach was used for synthesis of various derivatives of nido-carborane, including boron-containing biomolecules [3][4][5] and crown ethers [6,7]. At the same time, in the literature there are only a few examples of acyclic oxonium derivatives of polyhedral boron hydrides [8][9][10][11][12][13][14], and to the best of our knowledge, there are no examples of dimethyloxonium derivatives.…”

Section: Introductionmentioning

confidence: 99%

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Dimethyloxonium and Methoxy Derivatives of nido-Carborane and Metal Complexes Thereof

et al. 2019

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9-Dimethyloxonium, 10-dimethyloxonium, 9-methoxy and 10-methoxy derivatives of nido-carborane (9-Me2O-7,8-C2B9H11, 10-Me2O-7,8-C2B9H11, [9-MeO-7,8-C2B9H11]−, and [10-MeO-7,8-C2B9H11]−, respectively) were prepared by the reaction of the parent nido-carborane [7,8-C2B9H12]− with mercury(II) chloride in a mixture of benzene and dimethoxymethane. Reactions of the 9 and 10-dimethyloxonium derivatives with triethylamine, pyridine, and 3-methyl-6-nitro-1H-indazole result in their N-methylation with the formation of the corresponding salts with 9 and 10-methoxy-nido-carborane anions. The reaction of the symmetrical methoxy derivative [10-MeO-7,8-C2B9H11]− with anhydrous FeCl2 in tetrahydrofuran in the presence of t-BuOK results in the corresponding paramagnetic iron bis(dicarbollide) complex [8,8′-(MeO)2-3,3′-Fe(1,2-C2B9H10)2]−, whereas the similar reactions of the asymmetrical methoxy derivative [9-MeO-7,8-C2B9H11]− with FeCl2 and CoCl2 presumably produce the 4,7′-isomers [4,7′-(MeO)2-3,3′-M(1,2-C2B9H10)2]− (M = Fe, Co) rather than a mixture of rac-4,7′- and meso-4,4′-isomers.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dimethyloxonium and Methoxy Derivatives of nido-Carborane and Metal Complexes Thereof

et al. 2019

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“…The ring cleavage with other oxygen nucleophiles follows the usual pathway A corresponding to SN substitution. The previously reported reactions with phenolate ions led solely to pathway A and the corresponding phenols attached to the cage by a six atom linker [7,44]. Also reactions with 2-methoxy-phenol (guaiacol) as an example of naturally occurring compound and t-Bu-calix [4]arene, as an archetype for organic platform with four phenolic -OH sites, provided the expected products (9 − and 10 2− ) according to the pathway A, when the respective compounds were reacted with K 2 CO 3 and 1 in dry acetonitrile.…”

Section: Reaction Pathways Of 1 With Nucleophilesmentioning

confidence: 99%

“…Compounds of this type are sometimes referred to as "dumbbells" [43]. Similar double cluster compounds resulted also from reactions of 1 with dihydroxy benzenes as oxygen nucleophile [44]. These compounds were shown to adopt crown-ether like arrangements.…”

Section: Introductionmentioning

confidence: 99%

Focus on Chemistry of the 10-Dioxane-nido-7,8-dicarba-undecahydrido Undecaborate Zwitterion; Exceptionally Easy Abstraction of Hydrogen Bridge and Double-Action Pathways Observed in Ring Cleavage Reactions with OH− as Nucleophile

et al. 2020

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Ring cleavage of cyclic ether substituents attached to a boron cage via an oxonium oxygen atom are amongst the most versatile methods for conjoining boron closo-cages with organic functional groups. Here we focus on much less tackled chemistry of the 11-vertex zwitterionic compound [10-(O-(CH2-CH2)2O)-nido-7,8-C2B9H11] (1), which is the only known representative of cyclic ether substitution at nido-cages, and explore the scope for the use of this zwitterion 1 in reactions with various types of nucleophiles including bifunctional ones. Most of the nitrogen, oxygen, halogen, and sulphur nucleophiles studied react via nucleophilic substitution at the C1 atom of the dioxane ring, followed by its cleavage that produces six atom chain between the cage and the respective organic moiety. We also report the differences in reactivity of this nido-cage system with the simplest oxygen nucleophile, i.e., OH−. With compound 1, reaction proceeds in two possible directions, either via typical ring cleavage, or by replacement of the whole dioxane ring with -OH at higher temperatures. Furthermore, an easy deprotonation of the hydrogen bridge in 1 was observed that proceeds even in diluted aqueous KOH. We believe this knowledge can be further applied in the design of functional molecules, materials, and drugs.

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“…Currently, there are several methods for the preparation of mono-substituted nido -carboranes: C-substituted derivatives can be obtained by modification of the carborane cage at carbon atoms of the parent ortho -carborane followed by its deboronation to the corresponding nido -carborane. Last time, the most cited methods of synthesis B-substituted functional derivatives of nido -carboranes are ring opening of their cyclic oxonium derivatives under the action of nucleophilic agents [ 11 , 12 , 13 , 14 ], alkylation of their methylsulfide derivatives [ 15 , 16 , 17 , 18 ], Cu-promoted synthesis of their ammonium derivatives [ 19 ] and nucleophilic addition of alcohols and mercaptans to highly polarized triple bond B-N + ≡CR [ 20 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Nido-Carboranyl Azide and Its “Click” Reactions

et al. 2021

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Novel zwitter-ionic nido-carboranyl azide 9-N3(CH2)3Me2N-nido-7,8-C2B9H11 was prepared by the reaction of 9-Cl(CH2)3Me2N-nido-7,8-C2B9H11 with NaN3. The solid-state molecular structure of nido-carboranyl azide was determined by single-crystal X-ray diffraction. 9-N3(CH2)3Me2N-nido-7,8-C2B9H11 was used for the copper(I)-catalyzed azide-alkyne cycloaddition with phenylacetylene, alkynyl-3β-cholesterol and cobalt/iron bis(dicarbollide) terminal alkynes to form the target 1,2,3-triazoles. The nido-carborane-cholesterol conjugate 9-3β-Chol-O(CH2)C-CH-N3(CH2)3Me2N-nido-7,8-C2B9H11 with charge-compensated group in a linker can be used as a precursor for preparation of liposomes for Boron Neutron Capture Therapy (BNCT). A series of novel zwitter-ionic boron-enriched cluster compounds bearing a 1,2,3-triazol-metallacarborane-carborane conjugated system was synthesized. Prepared conjugates contain a large amount of boron atom in the biomolecule and potentially can be used for BNCT.

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Synthesis of podands with nido-carboranyl groups as a basis for construction of crown ethers with an incorporated metallacarborane moiety

Cited by 13 publications

References 42 publications

Dimethyloxonium and Methoxy Derivatives of nido-Carborane and Metal Complexes Thereof

Dimethyloxonium and Methoxy Derivatives of nido-Carborane and Metal Complexes Thereof

Focus on Chemistry of the 10-Dioxane-nido-7,8-dicarba-undecahydrido Undecaborate Zwitterion; Exceptionally Easy Abstraction of Hydrogen Bridge and Double-Action Pathways Observed in Ring Cleavage Reactions with OH− as Nucleophile

Synthesis and Structure of Nido-Carboranyl Azide and Its “Click” Reactions

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