Double Stereocontrol in α-Alkylation of Chiral Lithium Dienolates Generated from (E)-α,β-Olefinic Amides and Esters

Abstract

Abstract The methylation of the lithium dienolate generated from (E)-α,β-olefinic amide with Katsuki’s chiral auxiliary affords the α-methylated β,γ-enamide in an exceptionally high Z-selectivity (99%) over the terminal olefinic bond along with 99% de at the α-chiral center. The origin of the high Z-selectivity is discussed.