A novel and efficient procedure was introduced for the synthesis of alkyl acetates bearing arylthio and quinoxaline moieties 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. Moreover, 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.

A mild, efficient and stereoselective synthesis of dialkyl 2thiofumarates is described based on the addition reaction of aryl(benzyl) thiols and dialkyl acetylenedicarboxylates in the presence of triethylamine as a mild base. The reactions were stereoselectively performed in CH 2 Cl 2 at room temperature toward synthesis of Z-stereoimers as the major isomer in good yields.