A Decoupling Strategy for Position-Controlled Access to 1,3-Disubstituted Saturated Frameworks

The three-dimensional architecture and precise placement of functional groups critically influence the performance of drugs and functional materials, yet positional control on saturated carbocycles remains limited1–3. Framework editing, rather than de novo synthesis, offers an attractive strategy for direct site-selective synthesis of functionalized carbocycles. In particular, functional group translocation—migrating an existing substituent within a molecular framework without altering its core structure—has emerged as a powerful approach to access valuable substitution patterns in saturated systems4. However, its development has largely been confined to 1,2-5–10 and 1,4-migrations11,12. Here, we report a general and conceptually distinct platform for formal transannular 1,3-migration of aroyl groups across saturated carbocycles, enabling precise access to 1,3-disubstituted frameworks. This strategy proceeds via a neutral bicyclic intermediate generated by Norrish–Yang photocyclization, which is then oxidatively cleaved with hydrogenatom trapping. A distinctive feature is the coexistence of oxidant Mn(OAc)3 and a thiol reductant without their mutual quenching, enabling independent downstream reactivity. By decoupling cyclization from the migration event, this approach overcomes kinetic constraints that have historically precluded 1,3-translocation13. Broadly applicable to both radical and ionic pathways, this method enables ring expansion, scaffold hopping, distal editing through iterative translocation, and stereospecific modification of chiral substrates.