Orthoquinone monoketals A and orthoquinols B are cyclohexa-2, 4-dienone derivatives with valuable reactivity features for the construction of complex molecular architectures.[1] Their conjugated dienone unit and the vicinal positioning of their oxygenated functionalities constitute a unique structural arrangement that can be transformed rapidly into various kinds of polyoxygenated (poly) cyclic systems (Scheme 1).[1]