Palladium-Catalyzed Allylation of Endocyclic 1-Azaallyl Anions

Endocyclic 1-azaallyl anions engage allyl acetates in a palladium-catalyzed allylation followed by reduction to give unprotected 2-(hetero)aryl-3-allylpiperidines and 2-allyl-3-arylmorpholines, products not easily accessible by other means. The allyl group is then readily transformed into a variety of functional groups. Preliminary studies on the asymmetric variant of the reaction using an enantiomerically pure BI-DIME-type ligand provide the product with moderate enantioselectivity. Computational studies suggest that energy barriers of inner-sphere reductive elimination and outer-sphere nucleophilic substitution are almost the same, which makes both of them possible reaction pathways. In addition, the inner-sphere mechanism displays an enantiodiscriminating C-C bond forming step, while the outer-sphere mechanism is much less selective, which combined to give the asymmetric variant of the reaction moderate enantioselectivity.