Based on these observations we propose that radical 2b is trapped by Qu +• , instead of oxygen/superoxide, leading to the unstable aminal cation 2c. This aminal collapses to keto-sugar 2a releasing Qu (Scheme 4). Additional support for this mechanism is provided by the observation that with 2.5 F/mol the reaction under argon provided 70% conversion and with 1 F/mol 29% conversion was obtained. In conclusion, glycopyranosides can be electro-oxidized selectively at the C3 position in a quinuclidine-mediated process, which is highly complementary to the known electrochemical oxidation at C6 mediated by TEMPO. Whereas the quinuclidinium radical cation attacks the weakest C-H bond in a HAT process, TEMPO in its oxoammonium form oxidizes the primary hydroxy group because it is sterically most accessible.