Carbonyl-to-Silicon Exchange of Aromatic Lactones via Decarbonylation

Sila substitution, the strategy of replacing a specific carbon atom in organic molecules with silicon has garnered significant interest for the development of new functional compounds. However, the synthesis of silicon analogs remains challenging and is typically achieved through de novo methods. A promising alternative is the direct replacement of a carbon atom with silicon at a later stage of molecular construction. Here, we report a nickel-catalyzed carbonyl-to-silicon (CO-to-Si) atom swapping in lactones. Mechanistic studies reveal that the transformation proceeds via direct decarbonylation followed by silicon insertion. This method enables the efficient conversion of a broad range of lactones, including coumarins, isocoumarins, and dibenzopyranones, into their corresponding silacyclic analogs through decarbonylative silicon insertion. The resulting silacycles serve as versatile building blocks and undergo further derivatization. Notably, this strategy facilitates late-stage skeletal editing of pharmaceutical and natural product derivatives, providing a streamlined route to silicon-containing scaffolds from readily available lactones.