A direct and highly enantioselective reaction of N‐azidoacetyl‐1,3‐thiazolidine‐2‐thione with trimethyl orthoformate catalyzed by Tol‐BINAPNiCl2 in the presence of TESOTf and 2,6‐lutidine is reported. The heterocyclic scaffold can be easily removed by addition of a wide array of amines to give the corresponding enantiomerically pure 2‐azido‐3,3‐dimethoxypropanamides in high yields. Appropriate manipulation of the N‐benzyl amide derivative provides an efficient access to the antiepileptic agent lacosamide through a new enantioselective C−C bond‐forming process. DFT computational studies uncover clues for the understanding of the remarkable stereocontrol of the addition of a nickel(II) enolate to a putative oxocarbenium intermediate from trimethyl orthoformate.