Ring‐Retentive Allylation of Cyclopropanols Through Interception of Enolized Homoenolates by π‐Allylpalladium

Enolized homoenolates have emerged as distinct intermediates in cyclopropanol chemistry, enabling bond constructions beyond classical homoenolate and β‐keto radical manifolds. Their reactions with intrinsically electrophilic partners are established, but interception by catalytically generated electrophiles has remained unexplored. Herein, we report a palladium‐catalyzed, zinc‐mediated formal “allylic cyclopropylation” of cyclopropanols with allyl acetates. The reaction installs diverse allyl groups through transient ring opening to an enolized homoenolate, interception by π‐allylpalladium, and ring closure, thereby preserving the cyclopropane framework. An enantioselective variant, particularly effective for bicyclic substrates, demonstrates stereochemical control over these transient intermediates. Stereochemical experiments support a double‐inversion pathway characteristic of Tsuji–Trost reactivity. These findings integrate enolized homoenolates with transition‐metal catalysis and expand the scope of ring‐retentive cyclopropanol functionalization.