Journal ArticleDOI
Palladium-Catalyzed Selective Five-Fold Cascade Arylation of the 12-Vertex Monocarborane Anion by B-H Activation
Furong Lin,Jing-Lu Yu,Yunjun Shen,Shuo-Qing Zhang,Bernhard Spingler,Jiyong Liu,Xin Hong,Simon Duttwyler +7 more
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TLDR
A series of cage penta-arylated carboranes have been synthesized by palladium-catalyzed intermolecular coupling of the C-carboxylic acid of the monocarba- closo-dodecaborate anion with iodoarenes by direct cage B-H bond functionalization, setting a record in terms of one-pot directing group-mediated activation of inert bonds in a single molecule.Abstract:
A series of cage penta-arylated carboranes have been synthesized by palladium-catalyzed intermolecular coupling of the C-carboxylic acid of the monocarba-closo-dodecaborate anion [CB11H12]− with iodoarenes by direct cage B–H bond functionalization. These transformations set a record in terms of one-pot directing group-mediated activation of inert bonds in a single molecule. The methodology is characterized by high yields, good functional group tolerance, and complete cage regioselectivity. The directing group COOH can be easily removed during or after the intermolecular coupling reaction. The mechanistic pathways were probed using density functional theory calculations. A Pd(II)–Pd(IV)–Pd(II) catalytic cycle is proposed, in which initial coupling is followed by preferred B–H activation of the adjacent boron vertex, and continuation of this selectivity results in a continuous walking process of the palladium center. The methodology opens a new avenue toward building blocks with 5-fold symmetry.read more
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Controlled functionalization of o-carborane via transition metal catalyzed B–H activation
Yangjian Quan,Zuowei Xie +1 more
TL;DR: A review of recent advances in transition metal catalyzed vertex-specific BH functionalization of carbon-boron molecular clusters concludes that selection of a cage C-H bonds for functionalization is very challenging.
Journal ArticleDOI
Aggregation-Induced Electrochemiluminescence of Carboranyl Carbazoles in Aqueous Media
TL;DR: The results of cyclic voltammetry (CV) suggest that oxidation/reduction reactions take place at the carboranyl motif, and these compounds show a reductive-oxidative mechanism in contrast to other organic materials that show oxidative-reductive mechanisms.
Journal ArticleDOI
Metal-catalyzed cross-coupling chemistry with polyhedral boranes
TL;DR: This work has shown that the utility of metal-catalyzed cross-coupling can be extended to several classes of polyhedral borane including neutral and anionic carboranes, metallaboranes, and carbon-free boranes and 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.
Journal ArticleDOI
Catalytic Cascade Dehydrogenative Cross-Coupling of BH/CH and BH/NH: One-Pot Process to Carborano-Isoquinolinone.
TL;DR: The isolation and structural identification of a key intermediate, its controlled transformations and deuterium labelling experiments support a new Ir-nitrene mediated amination for B-H/N-H dehydrocoupling, suggesting the preferential occurrence of B-C cross-coupling over B-N one.
Journal ArticleDOI
Catalytic Regioselective Cage B(8)–H Arylation of o-Carboranes via “Cage-Walking” Strategy
TL;DR: On the basis of isolation of a key intermediate, deuterium labeling experiments and DFT calculations, a reaction mechanism involving a high-valent palladium induced "cage-walking" from B(4) to B(8) vertex is proposed to account for the regioselective B( 8)-H activation.
References
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Corwin Hansch,A. Leo,R. W. Taft +2 more
TL;DR: The Hammett equation has been widely used for the study and interpretation of organic reactions and their mechanisms as mentioned in this paper, and it is astonishing that u constants, obtained simply from the ionization of organic acids in solution, can frequently predict successfully equilibrium and rate constants for a variety of families of reactions in solution.
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Noncoordinating anions--fact or fiction? A survey of likely candidates.
Ingo Krossing,Ines Raabe +1 more
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