Silver‐Enabled Inverse Electron Demand Thermal Decarbonylative Skeletal Expansion: A New Gateway to the Synthesis of Multifunctionalized Quinoline

Herein, we have reported an efficient AgSbF 6 catalyzed decarbonylative tandem inverse electron demand hetero Diels–Alder reaction in a very moderate temperature for the construction of quinoline derivatives from 2‐(p‐tolyl)‐1H‐inden‐1‐one with a variety of internal alkynes. To understand the role of the Lewis acid in the reaction, highest occupied molecular orbital‐lowest unoccupied molecular orbital gaps are compared for the adducts formed between the diene and AgSbF 6 . A mechanistic investigation, utilizing density functional theory calculations, revealed a clear preference for the inverse electron demand hetero Diels–Alder reaction pathway. The release of carbon monoxide gas has been detected through headspace gas chromatography analysis. This strategy enables the one pot synthesis of quinoline derivatives which offer substantial potential in drug discovery.