At first, some alkyl 2-(arylthio)-2-(3-oxo-3,4-dihydroquinoxalin-2-yl)acetates derivatives were synthesized from the reaction of o-phenylenediamines, dialkyl acetylenedicarboxylates, and in-situ generated arylsulphenyl chlorides in DMF as solvent at room temperature. The procedure worked well for a variety of starting materials and the corresponding products were obtained in good yields. (Scheme 1). In continues, some derivatives of dialkyl 2-amino-3-thiomalates were stereoselectively synthesized via the reaction of amines, dialkyl acetylenedicarboxylates and in-situ generated arylsulphenyl chlorides in moderate to good yields in DCE as solvent at room temperature. (scheme 2).