AbstractThe asymmetric synthesis of α‐substituted α‐amino acids and propargylamines is described. As chiral auxiliary we used (S)‐(–)‐1‐dimethoxymethyl‐2‐methoxymethylpyrrolidine (SDMP,1). Treatment of the amino acids or amines with SDMP1afforded the corresponding amidinesC, which can be metalated and alkylated to yield the productsD, which were hydrolyzed to give the desired α‐substituted α‐amino acids20and propargylamines22. The method allows the enantioselective alkylation of amino acids and propargylamines in satisfactory chemical yields and fair to good enantioselectivity. The chiral auxiliary SDMP1is prepared from