Palladium-Catalyzed Benzene Arylation:  Incorporation of Catalytic Pivalic Acid as a Proton Shuttle and a Key Element in Catalyst Design

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 computa...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2006-12, Vol.128 (51), p.16496-16497
Main Authors: Lafrance, Marc, Fagnou, Keith
Format: Article
Language:English
Subjects:
Alkylation
Benzene - chemical synthesis
Benzene - chemistry
Catalysis
Catalysts: preparations and properties
Chemistry
Exact sciences and technology
General and physical chemistry
Molecular Structure
Organometallic Compounds - chemistry
Palladium - chemistry
Pentanoic Acids - chemistry
Protons
Stereoisomerism
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Summary: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% yield.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja067144j