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.
['Loh|Charles C J|CC|', 'Schmid|Matthias|M|', 'Peters|Brendan|B|', 'Fang|Xiang|X|', 'Lautens|Mark|M|http://orcid.org/0000-0001-9867-9178']
ring-opening reactions enantioselectivity heterocycles rhodium synthetic methods