Palladium-catalyzed cross-coupling reactions are state-of-the art methods for synthesis of many important compounds. The development of the use of the phenol-derived sulfonated hydroxyl group in the coupling reactions is highly attractive as the hydroxyl group is commonly present in organic compounds and they are versatile alternatives to aryl halides in cross-coupling reactions. In this tutorial review, we summarize the current development of palladium-catalyzed cross-coupling reactions of aryl mesylates.

Aminated adventures: The new phosphine ligand L in combination with a Pd(OAc)2 precursor provides the first palladium‐catalyzed amination of unactivated aryl mesylates. This catalyst system can be applied in an aqueous reaction medium without detrimental effect.

A decade advancement of transition metal-catalyzed borylation of aryl halides and sulfonates3

Aryl mesylates are found to be applicable as electrophiles in organosilicon-mediated coupling reactions. The catalyst system comprising 2 mol % of Pd(OAc)(2) and CM-phos supporting ligand is highly effective in catalyzing Hiyama cross-coupling of various aryl and heteroaryl mesylates. Interesting acid additive effects show that the presence of 0.25-0.50 equiv of acetic acid efficiently suppresses the mesylate decomposition and generally promotes the coupling product yields.

This study describes a new class of easily accessible indolyl phosphine ligands, prepared via an efficient protocol involving Fischer indolization from readily available phenylhydrazine and substituted acetophenones. This versatile ligand scaffold provides beneficial features, including high potential of steric and electronic tunability. The air-stable indolyl phosphines in combination with a palladium metal precursor provide highly effective catalysts for Suzuki-Miyaura coupling of unactivated aryl chlorides, and the catalyst loading down to 0.02 mol % can be achieved.