Electrochemical Functional‐Group‐Tolerant Shono‐type Oxidation of Cyclic Carbamates Enabled by Aminoxyl Mediators

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.