Enantioselective Mukaiyama-Michael Reaction of β,γ-Unsaturated α-Keto Esters with Silyl Ketene Acetals Catalyzed by a Chiral Magnesium Phosphate.

Abstract

We would like to describe an efficient and highly enantioselective Mukaiyama-Michael reaction of silyl ketene acetals with β,γ-unsaturated α-keto esters catalyzed by a chiral magnesium BINOL-derived phosphate. The resulting functionalized 1,5-dicarbonyl adducts are obtained in high yields (up to 96%) and with excellent enantioselectivities (up to 98%) under mild conditions. Two plausible mechanistic pathways were proposed, including a 1,4-addition and a hetero Diels-Alder [4 + 2] cycloaddition.