The first examples of palladium-catalyzed oxidative amination of unactivated alkyl olefins have been identified. To be successful, these reactions must be conducted under cocatalyst-free conditions that involve direct dioxygen-coupled turnover of the palladium catalyst. The oxidative amination products of norbornene and other cyclic alkenes implicate a cis-aminopalladation mechanism.

Facile and efficient: a palladium‐catalyzed intramolecular oxidative amination reaction [Eq. (1)] that uses molecular oxygen as a stoichiometric oxidant. These reactions require no cocatalyst for efficient reoxidation of the palladium, they operate in solvents ranging from heptane to dimethylsulfoxide, and achieve up to 250 turnovers (TO) and rates of 70 TO h−1.

Palladium(II) complexes catalyze the formation of enamides via the formal cross-coupling reaction between nitrogen nucleophiles and vinyl ethers. These vinyl transfer reactions proceed in good yields with amide, carbamate, and sulfonamide nucleophiles, and the optimal catalyst is (DPP)Pd(OCOCF(3))(2) (DPP = 4,7-diphenyl-1,10-phenanthroline). [reaction: see text]

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