Journal of the American Chemical Society, Vol.138, No.16, 5234-5237, 2016
Enantioselective gamma-Alkylation of alpha,beta-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement
A catalytic, enantioselective gamma-alkylation of alpha,beta-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed alpha-alkylation of an extended enolate, and a subsequent translocation of chirality to the gamma-position via a Cope rearrangement.