Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 10, Pages 3308-3311Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja1113936
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- NIH [GM-58108]
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Palladium-catalyzed direct arylations of benzene have been proposed to occur by the generation of a phosphine-ligated arylpalladium pivalate complex LPd(Ar)-(OPiv) and reaction of this complex with benzene. We have isolated an example of the proposed intermediate and evaluated whether this complex does react with benzene to form the biaryl products of direct arylation. In contrast to the proposed mechanism, no biaryl product was formed from cleavage of the benzene C H bond by LPd(Ar)-(OPiv). However, reactions of LPd(Ar)(OPiv) with benzene and additives that displace or consume the phosphine ligand formed the arylated products in good yield, suggesting that a ligandless arylpalladium(II) carboxylate complex undergoes the C-H cleavage step. Consistent with this conclusion, we found that reactions catalyzed by Pd(OAc)(2) without a ligand occur faster than, and with comparable selectivities to, reactions catalyzed by Pd(OAc)(2) and a phosphine ligand.
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