We report a scalable, one-pot Mannich route to enantioenriched alpha-amino esters by direct reaction of alpha-chloroglycine ester as a practical imino ester surrogate. The reaction is promoted by a chiral aminothiourea, which is proposed to operate cooperatively by generating an iminium ion by chloride abstraction and an enolate by deprotonation, followed by highly stereo-selective C-C bond formation between both reactive intermediates associated non-covalently within the catalyst framework