| The development and application of palladium-catalyzed methods for the amination of alkenes to form new carbon-nitrogen bonds are described herein. For intramolecular oxidative amination, a catalyst system consisting of 1:2 Pd(OAc)2/pyridine was optimal. This method for generating five-membered nitrogen-containing heterocycles was applied as a key step toward the total syntheses of proline-derived natural products (-)(alpha)-kainic acid and (+)-(alpha)-allokainic acid. Intermolecular oxidative amination of both aryl and aliphatic alkenes was achieved using catalytic palladium(II) acetate in benzonitrile. Both palladium-catalyzed oxidative animation systems utilize molecular oxygen as the stoichiometric oxidant with no need for a co-catalyst. In addition, enamides were generated by a redox neutral transfer vinylation reaction using vinyl ethers and catalytic (4,7-diphenyl-1,10-phenanthroline)palladium(II) trifluoroacetate. |
