Palucki M,
Buchwald SL.
* Massachusetts Institute of Technology, Cambridge, USA
Palladium-Catalyzed α-Arylation of Ketones.
J. Am. Chem. Soc. 1997;
119: 11108-11109
Key words
palladium catalysis - arylation - ketones
Significance
The palladium-catalyzed α-arylation of ketones was reported simultaneously and independently
by Buchwald and Hartwig (J. Am. Chem. Soc.
1997, 119, 12382). The use of BINAP or Tol-BINAP was necessary for this transformation, while
Hartwig employed ferrocene-based bisphosphines. Prior to these reports, α-arylation
required silyl enol ethers and lead and bismuth compounds.
Comment
The products were obtained in good to high yields. Excellent ratios of monoarylated
to diarylated products were obtained, as well as high regioselectivity and functional
group tolerance. The mechanism is proposed to occur through oxidative addition of
palladium(0) with the aryl bromide, ligand substitution by the sodium enolate, and
reductive elimination.
