Spatial Control Over Tether‐Tunable Coordination on Palladium for Divergent Synthesis of Bicyclo[n.1.0]alkanes via Oxidative Cyclopropanation of Enynes

Bicyclo[n.1.0]alkanes are highly valuable scaffolds in drug discovery and synthetic chemistry. However, their efficient and stereocontrolled construction remains a desirable yet challenging task. Herein, we report a palladium‐catalyzed oxidative cyclopropanation of 1,n‐enynes using cyclic malonyl peroxides as modular, tether‐tunable oxidants. This ligand‐free method enables divergent synthesis of three classes of bicyclo[n.1.0]alkanes with broad substrate scope, encompassing both oxygen‐ and nitrogen‐linked systems as well as sterically hindered trisubstituted alkenes. The transformation proceeds under mild conditions with high efficiency and stereospecificity, and an asymmetric variant achieves moderate yet promising enantiocontrol. Green metrics and biocompatibility assessments suggest that merging transition metal catalysis with cyclic malonyl peroxides may open avenues for sustainable and bio‐relevant synthetic strategies.