Programmable Synthesis of 1, n -Dicarbonyls Enabled by Photoinduced β-Fragmentation of Alkoxy Radicals from Cycloalkanols

Dicarbonyl architectures represent quintessential structural motifs, serving as versatile linchpins in organic synthesis and privileged scaffolds in pharmaceutical and natural product chemistry. Despite their ubiquity, a general, programmable strategy for the synthesis of diverse 1,n-dicarbonyls, particularly long-chain homologues, remains a formidable challenge, with existing methodologies often restricted to specific subtypes and suffering from operational constraints. Herein, we report a unified and innovative approach to address this long-standing synthetic bottleneck. By harnessing photoinduced alkoxy radicals derived from cycloalkanol precursors, employed as masked carbonyl synthons, we have developed a radical cascade manifold that seamlessly integrates β-fragmentation, Giese addition, and Kornblum oxidation. The strategic manipulation of the cycloalkanol ring size serves as a precise topological dial, enabling the programmable synthesis of 1,n-dicarbonyl compounds ranging from short- to long-chain variants.