A Cascade Rh(III)‐catalyzed C−H Activation/Chemodivergent Annulation of N‐carbamoylindoles with Sulfoxonium Ylides for the Synthesis of Dihydropyrimidoindolone and Tricyclic [1,3]Oxazino[3,4‐a]indol‐1‐ones Derivatives

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A highly efficient cascade Rh(III)‐catalyzed C−H activation/intramolecular chemodivergent cyclization reaction of N‐carbamoylindoles and sulfoxonium ylides has been successfully achieved for the first time. This synergistic process provides rapid access to functionalized dihydropyrimidoindolone and tricyclic [1,3]oxazino[3,4‐ a ]indol‐1‐ones skeletons under redox neutral conditions with broad substrate scope and remarkable functional‐group compatibility. Further late‐stage modification of structurally complex drug molecules and mechanistic studies were also accomplished. magnified image