Synthesis of Bridged Cyclopentane Derivatives by Catalytic Decarbonylative Cycloaddition of Cyclobutanones and Olefins

Herein, we report an intramolecular rhodium‐catalyzed decarbonylative coupling between cyclobutanones and alkenes that proceeds by C−C activation and provides a distinct approach to a diverse range of saturated bridged cyclopentane derivatives. In this reaction, cyclobutanones serve as cyclopropane surrogates, reacting in a formal (4+2−1) transformation. To demonstrate the efficacy of this method, it was applied in a concise synthesis of the antifungal drug Tolciclate. Decarbonylative “cut and sew”: An intramolecular decarbonylative coupling between cyclobutanones and alkenes has been developed that proceeds by rhodium‐catalyzed C−C activation and provides a distinct approach to a diverse range of saturated bridged cyclopentanes. In this formal (4+2−1) transformation, cyclobutanones serve as cyclopropane surrogates.