Avenue to novel <i>o</i>-carboranyl boron compounds – reactivity study of <i>o</i>-carborane-fused aminoborirane towards organic azides

Wang, Junyi; Xiang, Libo; Liu, Xiaocui; Matler, Alexander; Lin, Zhenyang; Ye, Qing

doi:10.1039/d4sc00489b

Cited by 7 publications

(1 citation statement)

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“…Several previous studies have been dedicated to generating icosahedral carborane-fused 2D carbo- and hetero-cycles as extensions of the carborane scaffolds. 17 These systems are interesting as they can provide new insights into questions of electronic delocalization between 2D and 3D aromatic scaffolds and give rise to structurally new heterocyclic motifs. 18 However, all-boron-vertex-bound icosahedral carborane-fused heterocycles bearing vicinal B–N bonds are still not accessible so far.…”

Section: Resultsmentioning

confidence: 99%

A Pd-catalyzed route to carborane-fused boron heterocycles

Zhu,

Wang,

et al. 2024

Chem. Sci.

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Section: Resultsmentioning

confidence: 99%

A Pd-catalyzed route to carborane-fused boron heterocycles

Zhu,

Wang,

et al. 2024

Chem. Sci.

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Antiaromatic 2-Azaboroles with π⁴σ² Electronic Configuration

Tan,

Chen,

Liu

et al. 2024

J. Am. Chem. Soc.

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Similar to pyridine, which is a structural analog of benzene, 2azaborole can be viewed as a structural analog of borole, in which the CH group at the 2-position is replaced by an N atom. Due to its unique π 4 σ 2 electronic configuration, it should exhibit Lewis acidity, antiaromaticity, as well as Lewis basicity simultaneously. However, this uniqueness also makes its synthesis and isolation particularly challenging. One anticipated issue is its readiness for self-dimerization. This work proposes 2-azaborole and targets the synthesis and characterization of its derivatives for the first time. By reacting benzoborirene C 6 H 4 {BN(SiMe 3 ) 2 } with bulky nitriles, crystalline benzo-fused 2-azaboroles have been successfully achieved and fully characterized. The importance of steric hindrance has been experimentally verified, showing that insufficient kinetic protection results in the dimerization of benzo-fused 2azaboroles to form BN-allenophanes, a class of 10-membered macrocyclic compounds featuring two BN-allene units. The unique electronic structure of 2-azaborole as well as the mechanism of dimerization has been corroborated by theoretical calculations. In addition, its ability to act both as a Lewis acid and a Lewis base is demonstrated through its reaction with 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene ( Me IiPr) and AlCl 3 , respectively, which also implies the potential of the 2-azaborole motif as a σ-donor ligand for main group and organometallic chemistry.

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Formal (2+2) ring expansion prevails over (4+2) cycloaddition of a kinetically stabilized benzoborirene with reactive cycloaddends

Sindlinger,

Biebl,

Ströbele

et al. 2024

Chem. Commun.

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Avenue to novel o-carboranyl boron compounds – reactivity study of o-carborane-fused aminoborirane towards organic azides

Abstract: Herein we report the reactivity study of o-carborane-fused bis(trimethylsilyl)aminoborirane towards three different types of organic azides, i.e., aryl, alkyl, and silyl azides. The reaction with ArN3 (Ar = 2,6-iPr2C6H4, 2,6-C6H3Cl2,...

Cited by 7 publications

References 60 publications

A Pd-catalyzed route to carborane-fused boron heterocycles

A Pd-catalyzed route to carborane-fused boron heterocycles

Antiaromatic 2-Azaboroles with π⁴σ² Electronic Configuration

Formal (2+2) ring expansion prevails over (4+2) cycloaddition of a kinetically stabilized benzoborirene with reactive cycloaddends

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Avenue to novel o-carboranyl boron compounds – reactivity study of o-carborane-fused aminoborirane towards organic azides

Abstract: Herein we report the reactivity study of o-carborane-fused bis(trimethylsilyl)aminoborirane towards three different types of organic azides, i.e., aryl, alkyl, and silyl azides. The reaction with ArN3 (Ar = 2,6-iPr2C6H4, 2,6-C6H3Cl2,...

Cited by 7 publications

References 60 publications

A Pd-catalyzed route to carborane-fused boron heterocycles

A Pd-catalyzed route to carborane-fused boron heterocycles

Antiaromatic 2-Azaboroles with π4σ2 Electronic Configuration

Formal (2+2) ring expansion prevails over (4+2) cycloaddition of a kinetically stabilized benzoborirene with reactive cycloaddends

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Antiaromatic 2-Azaboroles with π⁴σ² Electronic Configuration