The enantioselective palladium-catalyzed allylic alkylation with “soft”, stabilized carbanions is an established and versatile method today. “Hard”, preformed ketone enolates have been used for this purpose very reluctantly.

We have been able to react lithium and magnesium enolates of cyclohexanone with both substituted and unsubstituted allylic substrates. Thus, allylation products could be obtained in enantioselective or enantioselective and diastereoselective manner. It turns out that the presence of LiCl is crucial to reactivity and stereoselectivity. Remarkably, double allylation of the enolate and racemization of the product can be widely suppressed. The protocol was successfully applied to other cyclic ketones like cyclopentanone, 1-tetralone and 1-indanone as well as to acyclic aryl alkyl ketones.

In summary, it has been shown that π-allyl palladium complexes and preformed enolates, considered as incompatible for a long time, can indeed be combined in an efficient manner. Thus a new tool for diastereoselective and enantioselective C-C bond formation has become available.