Abstract
Single crystals of α‐methyl‐D‐glucopyranoside x‐irradiated at 12 K contain a primary alkoxy radical. In contrast to the previously characterized primary alkoxy radical found at 77 K, the C–O bond does not significantly reorient. This result, as well as deprotonation of an accompanying primary hydroxyalkyl radical, is explained by the presence of three, instead of the usual two, hydrogen bonds about the O6 atom.