Palladium(0)-Catalyzed Allylation of Highly Acidic and Nonnucleophilic Anilines. the Origin of Stereochemical Scrambling When Using Allylic Carbonates

Article abstract of DOI:10.1021/jo980209j

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.