Iron-Catalyzed Reductive Ring-Rearrangement Reaction of Bridged Benzo[b]oxocin-4-ones with Grignard Reagents to Afford Bridged Benzo[b]oxocin-2-ols

An iron-catalyzed reductive ring-rearrangement reaction of bridged benzo[b]oxocin-4-ones with Grignard reagents to produce bridged benzo[b]oxocin-2-ols is reported. Mechanistic studies indicate that an iron redox catalysis cycle involving oxidative addition to the C-O bond by low-valence iron and β-methoxyl elimination as key steps operates in this reaction.