Enantioselective Synthesis of α-Tertiary Hydroxyaldehydes by Palladium-Catalyzed Asymmetric Allylic Alkylation of Enolates

摘要

We report the first catalytic asymmetric synthesis of α-tertiary hydroxyaldehydes by palladium-catalyzed allylic alkylation of siloxy enol carbonates. The excellent selectivity toward aldehyde was achieved by using chiral ligand L, which is in stark contrast to dppe, which favors ketone formation. The reaction proceeds under very mild conditions and generates an α-tetrasub-stituted stereogenic center with excellent yield and enantiomeric excess. Further investigation of the mechanism, reaction scope, and its application in organic synthesis is ongoing.