Synthesis of crown ethers with the incorporated cobalt bis(dicarbollide) fragment

Kazakov, Grigoriy S.; Stogniy, Marina Yu.; Sivaev, Igor B.; Suponitsky, Kyrill Yu.; Godovikov, Ivan A.; Кирилин, А. Д.; Bregadze, V. I.

doi:10.1016/j.jorganchem.2015.05.012

Cited by 25 publications

(19 citation statements)

References 40 publications

(28 reference statements)

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“…[17] However, the complexation produces only small rotations of the dicarbollide ligands in the bis(phosphine) complexes (24.7 and 47.9°for the silver and gold complexes, respectively), whereas the structures of the metal-free thiacrowns have not been determined.…”

Section: Introductionmentioning

confidence: 99%

Methylsulfanyl‐Stabilized Rotamers of Cobalt Bis(dicarbollide)

et al. 2017

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Section: Introductionmentioning

confidence: 99%

Methylsulfanyl‐Stabilized Rotamers of Cobalt Bis(dicarbollide)

et al. 2017

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“…The ring cleavage with sodium hydrogen sulphide leads to nucleophilic substitution of type A resulting in a compound with a terminal -SH group [10-HS-(CH 2 -CH 2 O) 2 -nido-7,8-C 2 B 9 H 11 ] − (14 − ). This compound is identical with product that was prepared previously by two step procedure that comprised ring opening of 1 with thiourea followed by alkaline hydrolysis [45]. This derivative may be a good building block for bio-conjugation and has also potential for use in BNCT as easily available alternative of doubly charged [B 12 H 11 SH] 2− (BSH) [65].…”

Section: Reaction Pathways Of 1 With Nucleophilesmentioning

confidence: 81%

“…These compounds were shown to adopt crown-ether like arrangements. The reactions with other nucleophiles have been reported only for isomers of hydroxybenzoic acid [7], which lead to anionic products with one boron cage per molecule and thiourea [45].…”

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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“…Earlier we described the synthesis of symmetric 8,8′-dimethoxy derivative of cobalt bis(dicarbollide) [8,8′-(MeO)2-3,3′-Co(1,2-C2B9H10)2] − by alkylation of the corresponding dihydroxy derivative [53]. In this contribution we report synthesis of analogous paramagnetic 8,8′-dimethoxy derivative of iron bis(dicarbollide) K[8,8′-(MeO)2-3,3′-Fe(1,2-C2B9H10)2] (K [7]) by the reaction of K [3] with anhydrous FeCl2 in tetrahydrofuran in the presence of potassium tert-butoxide (Scheme 4). The 11 Indeed, the both dimethyloxonium derivatives of nido-carborane were found to N-methylate 3-methyl-6-nitro-1H-indazole, however, the results of these reactions were different (Scheme 3).…”

Section: Scheme 2 Demethylation Of Dimethyloxonium Derivatives Of Nimentioning

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%

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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Synthesis of crown ethers with the incorporated cobalt bis(dicarbollide) fragment

Cited by 25 publications

References 40 publications

Methylsulfanyl‐Stabilized Rotamers of Cobalt Bis(dicarbollide)

Methylsulfanyl‐Stabilized Rotamers of Cobalt Bis(dicarbollide)

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

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

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