Interception of Enolized Homoenolates by π-Allylpalladium: Ring-Retentive Allylation of Cyclopropanols

Enolized homoenolates have emerged as distinct reactive intermediates in the transformation of cyclopropanols, expanding bond constructions beyond classical homoenolate and β-keto radical manifolds. While their dual nucleophilic manifolds—as enolates and allylmetal equivalents—have been demonstrated with intrinsically electrophilic partners, their integration with catalytically generated electrophiles has remained unexplored. Herein, we report a palladium-catalyzed, zinc-mediated allylation of cyclopropanols that proceeds via interception of enolized homoenolates by a π-allylpalladium species. The reaction enables installation of various allyl groups while preserving the cyclopropane framework. Control experiments using a diastereodefined cyclohexenyl acetate support a double-inversion pathway characteristic of Tsuji–Trost reactivity. This selective capture of the enolate reactivity of the transient intermediate establishes a conceptual foundation for integrating enolized homoenolates with transition-metal catalysis.