Aerobic Allylic Amination Catalyzed by a Pd(OAc) 2 /P(OPh) 3 System with Low Catalyst Loading.

A Pd(OAc) 2 /P(OPh) 3 combination catalyzed Tsuji-Trost-type allylic amination under aerobic conditions. Both aromatic and aliphatic secondary amines were transformed into the corresponding allylic amines with a tiny amount of the catalyst system (typically 0.02 mol % Pd), only when allylic phosphates were employed as electrophiles. Other typical electrophiles, such as allylic acetate and carbonate, were marginally reactive. A Pd(0) complex, Pd[P(OPh) 3 ] 3 , formed in situ was suggested as an active species by mechanistic experiments.