Cooperative Palladium/Brønsted Acid Catalysis toward the Highly Enantioselective Allenylation of β‑Keto Esters

We report the first enantioselective allenylation of Pd enolates enabled by cooperative Pd/Brønsted acid catalysis employing β-keto esters and propargyl alcohols. The enantioselectivity originates solely from an in-situ-generated chiral metal enolate in an open transition state with no additional binding of the propargyl component to the catalyst. Thus a broad substrate scope was established, furnishing hitherto inaccessible products in very good yields with excellent enantioselectivities (up to >99:1 e.r.).