“…Based on previous mechanistic studies on MHAT reactions to alkenes 20,21 and our own work, 19 we indeed assumed that a fast, irreversible transfer of a hydrogen atom from highly reactive transient Fe(III)−H species to the carbohydrate olefin afforded the tertiary pseudoanomeric radical intermediate A (Scheme 7a). However, it was not clear if the key C−O bond-forming event proceeded through a radical process 27,29,30,45 (Scheme 7a, pathway A) or a cationic process (Scheme 7a, pathway B). Both pathways would lead to the same intermediates�the rather stable phenoxy radical D and finally to the phenolic O-ketoside product, possibly through a concerted proton-coupled electron transfer from an iron(II) ethanol complex.…”