An efficient synthesis of carboranyl tetrazoles via alkylation of 5-R-1H-tetrazoles with allylcarboranes

Ol’shevskaya, V. A.; Makarenkov, Anton V.; Kononova, Elena G.; Peregudov, Аlexander S.; Калинин, В. Н.

doi:10.1016/j.poly.2016.05.006

Cited by 9 publications

(7 citation statements)

References 86 publications

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“…The procedure for the synthesis of 3 was similar to that previously reported [40]. To a stirred solution of 9,10-I 2 -1,7-closo-C 2 B 10 H 10 2, (300 mg, 1.34 mmol) in THF (15 mL) cooled to 0 • C in an ice-water bath was added, drop wise, a solution of allylmagnesium chloride in THF (6.06 mL, 1 M, 6.06 mmol).…”

Section: Synthesis and Characterization Ofmentioning

confidence: 98%

“…To produce the B-C bonds on 1, a useful and general method is the Kumada cross-coupling reaction on B-iodinated m-carborane 2 with Grignard reagents in the presence of Pd(II) and Cu(I) catalysts. To achieve the di-branched m-carborane derivatives at the 9, 10 vertexes, the cross-coupling reaction on 2 was studied using CH 2 CHCH 2 MgCl Grignard derivative in the presence of [PdCl 2 (PPh 3 ) 2 ] and CuI as catalysts to give the 9,10-(CH 2 CHCH 2 ) 2 -1,7-closo-C 2 B 10 H 10 (3) in 95% yield [40].…”

Section: Synthesis Of Di-branched M-carborane Derivatives At the 910mentioning

confidence: 99%

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m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

et al. 2020

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Closo m-C2B10H12 can perform as a novel core of globular periphery-decorated macromolecules. To do this, a new class of di and tetrabranched m-carborane derivatives has been synthesized by a judicious choice of the synthetic procedure, starting with 9,10-I2-1,7-closo-C2B10H10. The 2a-NPA (sum of the natural charges of the two bonded atoms) value for a bond, which is defined as the sum of the NPA charges of the two bonded atoms, matches the order of electrophilic reaction at the different cluster bonds of the icosahedral o-and m- carboranes that lead to the formation of B-I bonds. As for m-carborane, most of the 2a-NPA values of B-H vertexes are positive, and their functionalization is more challenging. The synthesis and full characterization of dibranched 9,10-R2-1,7-closo-carborane (R = CH2CHCH2, HO(CH2)3, Cl(CH2)3, TsO(CH2)3, C6H5COO(CH2)3, C6H5COO(CH2)3, N3(CH2)3, CH3CHCH, and C6H5C2N3(CH2)3) compounds as well as the tetrabranched 9,10-R2-1,7-R2-closo-C2B10H8 (R = CH2CHCH2, HO(CH2)3) are presented. The X-ray diffraction of 9,10-(HO(CH2)3)2-1,7-closo-C2B10H10 and 9,10-(CH3CHCH)2-1,7-closo-C2B10H10, as well as their Hirshfeld surface analysis and decomposed fingerprint plots, are described. These new reported tetrabranched m-carborane derivatives provide a sort of novel core for the synthesis of 3D radially grown periphery-decorated macromolecules that are different to the 2D radially grown core of the tetrabranched o-carborane framework.

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Section: Synthesis and Characterization Ofmentioning

confidence: 98%

Section: Synthesis Of Di-branched M-carborane Derivatives At the 910mentioning

confidence: 99%

m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

et al. 2020

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“…This reaction is highly selective, and the hydrosilylation of ordinary double bonds results in the formation of 1-silyl-substituted derivatives. Recently, we developed an efficient approach for the preparation of boronated organosilicon derivatives 48,49 based on the application of allylcarboranes [50][51][52] as key compounds. Herein, we report the functionalization of the terminal double bonds in allylcarboranes with hydride-containing organosiloxane compounds via the Karstedt's catalyst hydrosilylation reaction.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of mono- and polyfunctional organosilicon derivatives of polyhedral carboranes for the preparation of hybrid polymer materials

et al. 2022

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“…Practical interest in B-halogenated carboranes has remained limited because of the reduced reactivity of the halogen atom . Recently, however, techniques have been developed that allow the creation of B–N and B–C bonds by cross-coupling according to the reactions of Kumada, , Suzuki, − and Heck − (see also refs and ). This approach opens up opportunities for the synthesis of new compounds with useful properties, including biologically active compounds. ,, …”

Section: Introductionmentioning

confidence: 99%

Noncatalytic Bromination of Icosahedral Dicarboranes: The Key Role of Anionic Bromine Clusters Facilitating Br Atom Insertion into the B–H σ-Bond

et al. 2021

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The mechanism of the noncatalytic bromination of carboranes was studied experimentally and theoretically. We found that the reactions of o- and m-carboranes 1 and 2 with elemental bromine are first order in the substrate but unusually high (approximately fifth) order in bromine. The calculated energy barriers of these reactions decrease sharply as more bromine molecules are added to the quantum-chemical system. A considerable primary deuterium kinetic isotope effect for the bromination of 2 indicates that the rate-limiting stage is B–H bond breakage. According to quantum-chemical reaction path calculations, the bond breakage proceeds after the intrusion of a bromine atom into the B–H σ-bond. The 9-Br and 9-OH substituents in carborane 1 strongly retard the bromination of the corresponding derivatives. The bromination mechanism of 9-OH-1 is complex and includes neutral, deprotonated, and protonated forms of the carborane. The high experimental kinetic reaction order in bromine, together with quantum chemical modeling, points to a specific mechanism of bromination facilitated by anionic bromine clusters which significantly stabilize the transition state.

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An efficient synthesis of carboranyl tetrazoles via alkylation of 5-R-1H-tetrazoles with allylcarboranes

Cited by 9 publications

References 86 publications

m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

Synthesis of mono- and polyfunctional organosilicon derivatives of polyhedral carboranes for the preparation of hybrid polymer materials

Noncatalytic Bromination of Icosahedral Dicarboranes: The Key Role of Anionic Bromine Clusters Facilitating Br Atom Insertion into the B–H σ-Bond

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