Synthesis and Derivatization of a Carbene‐Sulfinate Palladacycle

ABSTRACT An unprecedented C‐SO oxidative‐cleavage reaction was disclosed for fused thiazoline‐1‐oxide‐azolium salts with Ag 2 O to afford C carbene ^SO 2 palladacyclic complexes. The complex could undergo reversible redox reactions with Br 2 to afford an intermediary N‐heterocyclic carbene (NHC) complex with a sulfonyl bromide dangling group. This complex allowed divergent hydrolysis, alcoholysis, and aminolysis to prepare a series of sulfonate and sulfonamide functionalized NHC complexes and a C carbene ^NSO 2 palladacycle via further deprotonation. Selected complexes were employed in catalysis to show excellent activities in the aqueous Suzuki‐Miyaura coupling reactions and hydroamination reactions of aryl alkynes.