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Palladium-catalyzed benzene arylation: incorporation of catalytic pivalic acid as a proton shuttle and a key element in catalyst design.
Marc Lafrance,Keith Fagnou +1 more
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Experimental and computational evidence indicates that the pivalate anion is a key component in the palladium-pivalic acid cocatalyst system, that it lowers the energy of C-H bond cleavage and acts as a catalytic proton shuttle from benzene to the stoichiometric carbonate base.Abstract:
A palladium−pivalic acid cocatalyst system has been developed that exhibits unprecedented reactivity in direct arylation This reactivity is illustrated with the first examples of high yielding direct metalation−arylation reactions of a completely unactivated arene, benzene Experimental and computational evidence indicates that the pivalate anion is a key component in the palladation/C−H bond breaking event, that it lowers the energy of C−H bond cleavage and acts as a catalytic proton shuttle from benzene to the stoichiometric carbonate base Eight examples of substituted aryl bromides are included which undergo direct arylation with benzene in 55−85% yieldread more
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Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality.
TL;DR: A review of palladium-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle can be found in this paper.
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Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope.
TL;DR: This review summarizes the development and scope of carboxylates as cocatalysts in transition-metal-catalyzed C-H functionalizations until autumn 2010 and proposes new acronyms, such as CMD (concerted metalationdeprotonation), IES (internal electrophilic substitution), or AMLA (ambiphilic metal ligand activation), which describe related mechanisms.
Journal ArticleDOI
Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage.
TL;DR: P palladium and ruthenium catalysts have been described that enable the direct arylation of (hetero)arenes with challenging coupling partners--including electrophilic aryl chlorides and tosylates as well as simple arenes in cross-dehydrogenative arylations.
Journal ArticleDOI
C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals
TL;DR: This Review provides an overview of C-H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.
References
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Aryl-aryl bond formation one century after the discovery of the Ullmann reaction.
Journal ArticleDOI
Catalytic C−H/Olefin Coupling
Fumitoshi Kakiuchi,Shinji Murai +1 more
TL;DR: In this paper, the cleavage and addition of ortho C−H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitrile, and aldehydes to olefins and acetlylenes can be achieved with the aid of ruthenium catalysts.
Journal ArticleDOI
Anionic Pd(0) and Pd(II) intermediates in palladium-catalyzed Heck and cross-coupling reactions.
Christian Amatore,Anny Jutand +1 more
TL;DR: The anion ligated to the palladium(0) affects the kinetics of the oxidative addition to ArI as well as the structure and reactivity of the arylpalladium(II) complexes produced in this reaction.
Journal ArticleDOI
Catalytic intermolecular direct arylation of perfluorobenzenes.
TL;DR: Penta-, tetra-, tri-, and difluorobenzenes undergo direct arylation with a wide range of arylhalides in high yield and utilize commercially available, air-stable catalyst precursors.
Journal ArticleDOI
Catalytic direct arylation with aryl chlorides, bromides, and iodides: intramolecular studies leading to new intermolecular reactions.
TL;DR: Mechanistic investigations have provided insight into the catalyst's mode of action and show the presence of a kinetically significant C-H bond cleavage in palladium-catalyzed direct arylation of simple arenes, opening the door for the development of other new direct aRYlation processes.