An interrupted Corey-Chaykovsky reaction of designed azaarenium salts: synthesis of complex polycyclic spiro- and fused cyclopropanoids

Simultaneous dearomatizing spirannulation of pyridinium salts is still in its infancy. Here, we present an organized skeletal remodeling of designed pyridinium salts by utilizing an interrupted Corey-Chaykovsky reaction to access unprecedented and structurally intriguing molecular architectures such as the vicinal bis-spirocyclic indanones and spirannulated benzocycloheptanones. This hybrid strategy rationally merges the nucleophilic features of sulfur ylides with the electrophilic pyridinium salts to achieve the regio- and stereoselective synthesis of new classes of cyclopropanoids. The plausible mechanistic pathways were derived from experimental results and control experiments.

Automated summary

In this study, a structured remodeling of designed pyridinium salts was achieved through an interrupted Corey-Chaykovsky reaction, leading to the synthesis of unprecedented multi-ring compounds such as vicinal bis-spirocyclic indanones and spirannulated benzocycloheptanones. By rationally combining nucleophilic sulfur ylides with electrophilic pyridinium salts, a regio- and stereoselective synthesis of new classes of cyclopropanoids was achieved. Plausible mechanistic pathways were proposed based on experimental results and control experiments.