Programmable Synthesis of 1,n-Dicarbonyls Enabled by Photoinduced β-Fragmentation of Alkoxy Radicals from
Yiman Gao1, Kui Zhang1, Lingchao Cai1
1State Key Laboratory for Development and Utilization of Forest Food Resources, Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China.
Abstract:
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.
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