Palladium-Catalyzed Selective Five-Fold Cascade Arylation of the 12-Vertex Monocarborane Anion by B–H Activation

Lin, Furong; Yu, Jinpeng; Shen, Yunjun; Zhang, Shuo‐Qing; Spingler, Bernhard; Liu, Jiyong; Hong, Xin; Duttwyler, Simon

doi:10.1021/jacs.8b07872

Cited by 85 publications

(23 citation statements)

References 162 publications

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“…This approach was used to install five aryl groups onto [1-COOH-CB 11 H 11 ] 1− at B-H vertices adjacent to the carboxylic acid directing group metal-catalyzed B-H activation. 29 Similar metal-catalyzed B-H polyfunctionalization strategies were reported for 10- and 12-vertex polyhedral boranes. 24,31,33…”

Section: Mechanistic Considerations Of Metal-catalyzed Polyhedral Bor...mentioning

confidence: 63%

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

2019

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Over the past several decades, metal-catalyzed cross-coupling has emerged as a very powerful strategy to functionalize carbon-based molecules. More recently, some of the cross-coupling methodologies have been adapted to inorganic compounds including boron-rich clusters. The development of this chemistry relies on the ability to synthesize halogenated boron-rich clusters which can serve as electrophilic cross-coupling partners with nucleophilic substrates in the presence of a metal catalyst. While the cross-coupling chemistry with boron-clusters is conceptually reminiscent to that of its hydrocarbon counterparts, several key aspects including the spheroidal bulk of clusters, and the distinct nature of boron-halogen / boron-heteroatom bonds make this chemistry unique. The utility of metal-catalyzed cross-coupling can be extended to several classes of polyhedral boranes including neutral and anionic carboranes, metallaboranes, and carbon-free boranes. Importantly, cross-coupling enables a suite of boron-heteroatom (C, N, O, P, S) couplings to prepare boron cluster-based systems that can be used for ligand design, medicinal chemistry, and materials applications.

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Section: Mechanistic Considerations Of Metal-catalyzed Polyhedral Bor...mentioning

confidence: 63%

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

2019

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“…Very recently, our group reported a cascade dehydrocoupling strategy to prepare carborano‐isoquinolinones from readily available carborane and benzamide . Such a protocol possesses considerable advantages including better atom/step economy, functional group tolerance and practicability, in comparison with conventional transition‐metal‐catalyzed B—H functionalization reactions of carboranes, which require pre‐functionalized coupling partners. Inspired by this, we initiated an investigation of catalytic cascade dehydrocoupling of carborane with benzoic acid.…”

Section: Background and Originality Contentmentioning

confidence: 99%

One‐Pot Process to Carborano‐Coumarin via Catalytic CascadeDehydrogenative Cross‐Coupling

Lyu

Quan

et al. 2020

Chin. J. Chem.

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Summary of main observation and conclusion Ir‐catalyzed cascade dehydrogenative CH/BH and BH/OH cross‐coupling of carboranyl carboxylic acid with readily available benzoic acid has been achieved, leading to the facile synthesis of previously unavailable carborano‐coumarin in a simple one‐pot process. Two cage B—H, one aryl C—H and one O—H bonds are activated to construct efficiently new B—C and B—O bonds. The cascade cyclization can stop at the first B—H/C—H cross‐coupling step by tuning the reaction conditions, resulting in a series of α‐carboranyl benzoic acid and aryl carborane derivatives. Control experiments indicate that B—H/C—H dehydrocoupling proceeds preferentially over B—H/O—H dehydrocoupling, and both directing groups and oxidants are crucial for this reaction. An iridium(V) intermediate is proposed to be involved in the catalytic cycle.

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“…Very recently, Duttwyler et al. reported intermolecular coupling of the 1‐ C ‐carboxylic acid of C1 carborane anion 20 with iodoarenes 28 by direct cage B−H bond activation with a palladium catalyst (Scheme A) . This directing method could activate five equivalent inert B−H bonds within a single molecule, and provided access to a wide range of cage penta‐arylated C1 carborane anion derivatives 29 .…”

Section: Recent Advances In Synthetic Chemistry At the Boron Verticesmentioning

confidence: 99%

Recent Progress in the Synthesis of the Monocarba‐closo‐dodecaborate(−) Anions

Kanazawa

Kitazawa

Uchiyama

2019

Chemistry A European J

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This Concept article focuses on the rapid growth in studies of the chemistry of the monocarba‐closo‐dodecaborate(−) anion (C1 carborane anion). As one of the most stable anions known, the C1 carborane anion has been useful for exploring the chemistry of highly reactive cations. On the other hand, development of novel functional molecules utilizing the unique properties of C1 carborane anion (e.g., σ‐aromaticity, rigid spherical skeleton) has progressed more slowly. The main reason for this is the relatively undeveloped state of synthetic chemistry in this area. Recent advances in the synthetic chemistry of C1 carborane anion are highlighted in this Concept article, focusing on cross‐coupling reactions at the carbon vertex, direct conversion of B−H bonds, and the synthesis of multivalent weakly coordinating anions. These progressions move this species beyond its well‐established role of highly stable “counter” monocharged anion.

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Palladium-Catalyzed Selective Five-Fold Cascade Arylation of the 12-Vertex Monocarborane Anion by B–H Activation

Cited by 85 publications

References 162 publications

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

One‐Pot Process to Carborano‐Coumarin via Catalytic CascadeDehydrogenative Cross‐Coupling

Recent Progress in the Synthesis of the Monocarba‐closo‐dodecaborate(−) Anions

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