Kinetic resolution, nucleophilic substitution asymmetric allylation

An interesting use of the nickel-catalyzed allylic alkylation has prochiral allylic ketals as substrate (Scheme 8E.47) [206]. In contrast to the previous kinetic-resolution process, the enantioselectivity achieved in the ionization step is directly reflected in the stereochemical outcome of the reaction. Thus, the commonly observed variation of the enantioselectivity with respect to the structure of the nucleophile is avoided in this type of reaction. Depending on the method of isolation, the regio- and enantioselective substitution gives an asymmetric Michael adduct or an enol ether in quite good enantioselectivity to provide further synthetic flexibility. 

Gais H, Jagusch T, Spalthoff N, Gerhards F, Frank M, Raabe G. Highly selective palladium catalyzed kinetic resolution and enantioselective substitution of racemic allylic carbonates with sulfur nucleophiles asymmetric synthesis of allylic sulfides, allylic sulfones, and allylic alcohols. Chem. Eur. J. 2003 9 4202-A221. 

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