An efficient methodology has been developed for the one-pot or telescoped synthesis of aliphatic sulfonamides, sulfonyl fluorides, and unsymmetrical sulfones on the basis of interrupted alkylation of sodium hydroxymethylsulfinate (rongalite) with alkyl halides. The protocols are conducted under mild conditions, use inexpensive and shelf-stable reagents, and are not sensitive to air/moisture. These conditions can be applied in rapid parallel chemical synthesis, which was demonstrated by the preparation of a small sulfonamide library based on the core structure of the anticoagulant drug Tirofiban.