Electrophilic Activation of [1.1.1]Propellane for the Synthesis of Nitrogen‐Substituted bicyclo[1.1.1]pentanes

Strategies commonly used for the synthesis of functionalised bicyclo[1.1.1]pentanes (BCP) rely on reaction [1.1.1]propellane with anionic or radical intermediates. In contrast, electrophilic activation has remained a considerable challenge due to facile decomposition BCP cations, which severely limited applications this strategy. Herein, we report in halogen bond complex, enables its electron-neutral nucleophiles such as anilines and azoles give nitrogen-substituted BCPs that are prominent motifs drug discovery. A detailed computational analysis indicates key bonding interaction promotes nucleophilic attack without sacrificing cage stabilisation. Overall, our work rehabilitates valuable strategy accessing BCPs.