Exploiting Distal Reactivity of Coumarins: A Rhodium‐Catalyzed Vinylogous Asymmetric Ring‐Opening Reaction

While the utility of vinylogous enolates is well established in the setting of vinylogous aldol, Mannich, and Michael chemistries, literature reports concerning γ-reactivity are scarce for other reaction classes. Presented herein is an unprecedented example of vinylogous reactivity exemplified by the rhodium-catalyzed asymmetric ring-opening reaction of oxabicycles. This strategy also provides a powerful route to incorporate the biologically useful coumarin motif into the hydronapthalene scaffold.