N-O Dual Functional Group Transposition via Energy Transfer Photocatalysis

Molecular editing and skeletal remodeling have emerged as highly innovative and synthetically efficient strategies. Within this context, functional group translocation facilitates streamlined synthesis and direct access to unique molecular scaffolds. While research in this area has largely centered on single-group transposition, dual functional group transposition (dFGT) remains underdeveloped due to the demanding requirement for stringent chemo- and regioselectivity control. Here, we report a photocatalytic energy transfer (EnT) strategy that achieves dFGT through precisely regulated radical sorting, governing the sequence of migration and coupling events. This approach is applicable to both activated and unactivated alkyl derivatives for N-O dFGT. Combined theoretical and experimental studies reveal a mechanism involving EnT-driven decarboxylative diradical generation, followed by 1,2-phosphatoxy migration, and culminating in radical-radical coupling. Furthermore, this methodology has been successfully extended to N-N dFGT, demonstrating its general applicability.