Stereo- and Regiochemistry in Palladium-Catalyzed Nucleophilic Substitution of Optically Active (E)- and (Z)-Allyl Acetates

Article abstract of DOI:10.1021/jo00355a025

Optically acive (E)- and (Z)-allyl acetates, 3-acetoxy-1-phenyl-1-butene (1) and its regioisomer, 1-acetoxy-1-phenyl-3-butene (2), were allowed to react with sodium dimethyl malonate, sodium acetylacetonate, and sodium methyl acetoacetate in the presence of a palladium catalyst.The reaction of (E)-acetates proceeded with retention of configuration and that of (Z)-acetates proceeded with inversion accompanied by geometrical isomerization from Z to E.The stereochemistry observed in the reaction with phenylzinc bromide was opposite to that with the soft nucleophiles.