Despite the great versatility of the sulfonyl group in organic synthesis, it is surprising that the overwhelming majority of reported applications are restricted to phenylsulfonyl- or tosyl-derived substrates. Since recently, our research group is engaged in exploring the reactivity of heteroarylsulfonyl substrates, mainly N-sulfonyl imines and unsaturated sulfones, as achiral templates in transition metal-catalyzed transformations. Due to its metal-coordinating capability, the heteroarylsulfonyl functionality acts as a catalyst-directing functionality, thereby producing a strong acceleration of the reaction. In particular, the (2-pyridyl)sulfonyl group and related nitrogen-containing heteroarylsulfonyl moieties were found to provide exceptional levels of reactivity and/or selectivity in a number of transition metal-catalyzed reactions, such as the palladium- and copper-catalyzed multiple arylation of allyl sulfones or the copper-catalyzed direct alkylation of N-sulfonyl imines whith organozinc bromides. Some innovative asymmetric catalysis applications have also been developed based on this strategy, such as the chiral Lewis acid-catalyzed inverse-electron-demand Diels-Alder reaction of N-sulfonyl 1-azadienes or the copper-catalyzed conjugate reduction of Β,Β–disubstituted–Α,Β–unsaturated sulfones (see Scheme below). The N,N-bidentate character of N-(2-pyridyl)sulfonyl imines towards metal-coordination (through the imino and pyridyl nitrogens) has been demonstrated by X-ray crystallography.