In the present study, a new synthetic strategy towards N-acylated glycinamides was developed by the use of 1,3,5-triazinanes as formaldimine surrogates in the Ugi reaction. The targeted products were obtained in a combinatorial, diversity-oriented fashion in good yields. Further modifications allowed us to adapt this procedure for the one-pot two-step syntheses of a local anesthetic druglidocaine and several unsymmetrically substituted diketopiperazines.