Pyrimidin‐2‐yl sulfonates, as a reaction partner, can be easily prepared from inexpensive commercial materials and are efficiently cross‐coupled with arylboronic acids and terminal alkynes by using Pd(OAc)2‐catalyzed Suzuki and Sonogashira reactions. A wide array of C2‐functionalized pyrimidines have been prepared in good to excellent yields. 2‐Arylpyridines and 2‐(oct‐1‐ynyl)pyridine were also synthesized.

An efficient method for carbon-carbon bond formation is described. The process employs the palladium-catalyzed copper-mediated cross-coupling of diheteroaryl disulfides with arylboronic acids or alkynes to deliver C À C coupling products through unreactive C À S bond cleavage. The scope of the coupling reactions, including both the disulfides and arylboronic acids or alkynes, are documented.

Pyrimidin‐2‐yl sulfonates, as an efficient reaction partner, which can be easily prepared from cheap commercial materials, were coupled with phenols and anilines to give a wide array of C2‐aryloxy‐ and arylaminopyrimidines in good to excellent yields under mild reaction conditions.