A general photoinduced manganese-catalyzed platform for the sequential difunctionalization of [1.1.1]propellane

Bicyclo[1.1.1]pentanes (BCPs) constitute prominent bioisosteric replacements for aromatic frameworks and are frequently incorporated into diverse pharmaceutical compounds. However, current synthetic routes, especially those for the synthesis of sulfonyl BCP derivatives, are hampered by narrow substrate scope and limited functional group tolerance. These constraints underscore the demand for more versatile and operationally practical synthetic strategies. Here, we disclose a general photoinduced manganese-catalyzed platform for the sequential difunctionalization of [1.1.1]propellane, enabling the modular synthesis of multifunctional sulfonyl BCPs. This platform facilitates the construction of diverse sulfonyl-BCP derivatives, including ─Cl, ─Br, ─I, ─CN, ─SCD ₃ , ─H, ─HetAr, ─COAr, ─SAr, ─N═NAr, etc., with exceptional functional group tolerance and scalability. The utility of this approach is further enhanced by its applicability to late-stage functionalization of pharmacologically active compounds and derivative synthesis. Mechanistic investigations and DFT calculation revealed that this work involves the ligand-accelerated manganese-catalyzed halogen-atom transfer (XAT) radical addition process.