Complete Retention of Z Geometry in Allylic Substitution Catalyzed by an Iridium Complex

The Z geometry of methyl ( Z )-3-monosubstituted-2-alkenyl carbonate was completely retained in iridium complex-catalyzed allylic amination. The reaction of methyl ( Z )-2-nonenyl carbonate with piperidine in the presence of a catalytic amount of [Ir(COD)Cl] 2 and P(OPh) 3 at 50 °C for 2 h gave a 98:2 mixture of ( Z )-1-(2-nonenyl)piperidine and 1-(1- n -hexyl-2-propenyl)piperidine in 86% yield. No E isomer was obtained. Various ( Z )-allylic amines were obtained in 91−100% selectivity by allylic amination of methyl ( Z )-3-monosubstituted-2-alkenyl carbonate.