Highly Enantioselective Michael Addition of α‐Substituted Cyano Ketones to β,γ‐Unsaturated α‐Keto Esters using Bifunctional Thiourea‐Tertiary Amine Catalysts: An Easy Access to Chiral Dihydropyrans

An asymmetric Michael addition of α‐substituted cyano ketones to β,γ‐unsaturated α‐keto esters to form chiral dihydropyrans catalyzed by a series of α‐amino acid‐derived thiourea‐tertiary amines is presented. A novel tyrosine‐derived thiourea catalyst was identified as the optimal catalyst providing the desired product in 91–95% yields and with 90–96% ee at a low catalyst loading of 2.0 mol%. The utility of the reaction was exemplified by facile conversion of the dihydropyran product into pharmaceutically useful dihydropyridine.