Pyridyl Pyrimidylsulfones as Latent Pyridyl Nucleophiles in Palladium-Catalyzed Cross-Coupling Reactions

We introduce pyridyl pyrimidylsulfones as latent, efficient pyridyl nucleophiles for Pd-catalyzed cross-coupling reactions with (hetero)aryl bromides. The reaction proceeds via an S_NAr process, generating sulfinates in situ, followed by desulfinative cross-coupling in the presence of Pd catalyst, phenol, and cesium carbonate. This method provides access to a wide range of (hetero)arylpyridine derivatives and enables late-stage functionalization, addressing limitations commonly associated with pyridylboron reagents in Pd-catalyzed cross-coupling. Additionally, the pyrimidylsulfones demonstrate compatibility with multistep substrate elaboration, as evidenced by the successful bidirectional functionalization of the pyridine ring, yielding teraryl compounds.