1,4-Additions of arylboron, -silicon, and -bismuth compounds to α,β-unsaturated carbonyl compounds catalyzed by dicationic palladium(II) complexes

Yamamoto, Yasunori; Nishikata, Takashi; Miyaura, Norio

doi:10.1351/pac200880050807

Pure Appl. Chem., 2008, Vol. 80, No. 5, pp. 807-817

http://dx.doi.org/10.1351/pac200880050807

1,4-Additions of arylboron, -silicon, and -bismuth compounds to α,β-unsaturated carbonyl compounds catalyzed by dicationic palladium(II) complexes

Yasunori Yamamoto¹, Takashi Nishikata² and Norio Miyaura¹

¹ Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
² Innovation Plaza Hokkaido, Japan Science and Technology Agency, Sapporo 060-0819, Japan

Abstract: An enantioselective synthesis of cyclic and acyclic β-aryl ketone and aldehydes via Pd(II)-catalyzed 1,4-addition of Ar-m [m = B(OH)₂, BF₃K, Si(OMe)₃, SiF₃, BiAr₂] to α,β-unsaturated ketones or aldehydes is described. The catalytic cycle involves transmetallation between Ar-m and Pd complexes as a key process, the mechanism of which is discussed on the basis of characterization of the transmetallation intermediate and electronic effect of the substituents. The enantioselection mechanism and efficiency of a chiraphos ligand for structurally planar α,β-unsaturated ketones are discussed on the basis of the X-ray structure of the catalyst and results of density functional theory (DFT) computational studies on the model of coordination of the substrates to the phenylpalladium(II)/(S,S)-chiraphos intermediate.