Nickel‐Catalyzed Cross Coupling of <i>N</i> ‐Alkenyl Heterocycles and Aryl Sulfonium Salts: Expedient Access to <i>N</i> ‐Benzyl Heterocycles

A nickel‐catalyzed system is developed that enables the coupling between aryldibenzothiophenium salts and N ‐alkenyl heterocycles. Traditionally, medicinally relevant N ‐benzylic heterocycles are constructed via harsh substitution conditions between the N‐H heterocycle and a benzyl electrophile in the presence of strong bases. The CC cross coupling strategy presents attractive potential for the synthesis of these important scaffolds, e.g., carboetomidate. Herein, it is documented that the combination of a site‐selective CH dibenzothiophenation with a nickel‐catalyzed C(sp 3 )–C(sp 2 ) cross coupling grants access to a diverse range of synthetically useful N ‐benzylic heterocycles, i.e., alkylated arenes. In particular, the mild conditions and good functional group compatibility permit the rapid assembly of molecular complexity and late‐stage functionalization of bioactive compounds, such as clofibrate, fenofibrate, and fenbufen, thus providing an orthogonal protocol to existing S N 2 and CN coupling approaches.