A new methylation of N,S-atoms using dimethyl sulfite as a safe and cheap methylating reagent through halogen bond promoted ring-opening coupling of benzothiazoles is described.

A novel and efficient method for the synthesis of methyl sulfone derivatives via palladium-catalyzed methylsulfonylation of alkyl halides with dimethyl sulfite has been described. A variety of aryl and alkyl iodides underwent the sulfonylation smoothly to furnish methyl sulfites in moderate to excellent yields.

A tetramethylammonium iodide (TBAI)-mediated cyclization and methylsulfonylation of propargylic amides enabled by dimethyl sulfite as a SO2 surrogate and methyl source have been developed. The transition metal-free and oxidant-free reaction provides a practical and efficient approach for the selective synthesis of methylsulfonyl oxazoles in moderate to excellent yields with good functional group compatibility.