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Electrochemical Functional-Group-Tolerant Shono-type Oxidation of Cyclic Carbamates Enabled by Aminoxyl Mediators
Fei Wang1, Mohammad Rafiee1, Shannon S Stahl1
1Department of Chemistry, University of Wisconsin-Madison, Madison, WI, 53706, USA.
Abstract:
An electrochemical method has been developed for α-oxygenations of cyclic carbamates by using a bicyclic aminoxyl as a mediator and water as the nucleophile. The mediated electrochemical process enables substrate oxygenation to proceed at a potential that is approximately 1 V lower than the redox potential of the carbamate substrate. This feature allows for functional-group compatibility that is inaccessible with conventional Shono oxidations, which proceed by direct electrochemical substrate oxidation. This reaction also represents the first α-functionalization of non-activated cyclic carbamates with oxoammonium oxidants.
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