Direct Catalytic Asymmetric Mannich-type Reaction of α,β-Unsaturated γ-Butyrolactam with Ketimines.

We report a direct catalytic asymmetric Mannich-type addition of α,β-unsaturated γ-butyrolactam to α-ethoxycarbonyl ketimines promoted by a soft Lewis acid/Brønsted base cooperative catalyst. A thiophosphinoyl group on the nitrogen of ketimines was crucial for both electrophilic activation and α-addition of γ-butyrolactams. The obtained aza-Morita-Baylis-Hillman-type products bear an α-amino acid architecture with a tetra-substituted stereogenic center.