title: Palladium(0)-Catalyzed Allylation of Highly Acidic and Nonnucleophilic Anilines. The Origin of Stereochemical Scrambling When Using Allylic Carbonates.
abstract: Acidic anilines such as diphenylamine, phenothiazine, and nitroanilines are efficiently allylated under palladium catalysis using allyl carbonates as allylating reagents. A stereochemical study of the reactions of ethyl cis-5-methyl-2-cyclohexenylcarbonate with 4-nitro- and 2,4-dinitroaniline was performed. Bidentate phosphines as stabilizing ligands gave clean retention of configuration whereas triphenylphosphine permitted cis-trans isomerization of the allylic carbonate, the allylation reactions occurring under Curtin-Hammet preequilibrium conditions.
authors.affiliation: Department of Chemistry, Universitat Autònoma de Barcelona, Cerdanyola, 08193-Barcelona, Spain.
authors.forename: Marcial
authors.initials: M
authors.lastname: Moreno-Mañas
authors.forename: Lurdes
authors.initials: L
authors.lastname: Morral
authors.forename: Roser
authors.initials: R
authors.lastname: Pleixats