Over the past years, significant progress has been made in the site-selective modification of unprotected and partially protected carbohydrates. Because of its versatility regarding further modifications, regioselective oxidation is particularly noteworthy. 2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO)-mediated oxidation of glycopyranosides leads to selective oxidation of the primary C6 hydroxy group, most often producing the corresponding uronic acids. Palladiumcatalyzed oxidation and hydrogen atom-transfer (HAT) reactions show a strong preference for the secondary C3 hydroxy group (Scheme 1), and a rationale for this has been provided. Scheme 1. Site-selective oxidation of methyl-a-D-glucopyranoside (1). The C3 selective oxidation, in particular the palladium-catalyzed version, has shown to be versatile and scalable, but for many applications a precious metal-free protocol would be a gain.