10.1021/ja067144j.s001
Marc Lafrance
Marc
Lafrance
Keith Fagnou
Keith
Fagnou
Palladium-Catalyzed Benzene Arylation: Incorporation of Catalytic Pivalic
Acid as a Proton Shuttle and a Key Element in Catalyst Design
American Chemical Society
2006
Catalytic Pivalic
aryl bromides
proton shuttle
Key Element
stoichiometric carbonate base
reactivity
arylation
unactivated arene
Proton Shuttle
pivalate anion
benzene
bond
2006-12-27 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Palladium_Catalyzed_Benzene_Arylation_Incorporation_of_Catalytic_Pivalic_Acid_as_a_Proton_Shuttle_and_a_Key_Element_in_Catalyst_Design/3038530
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.