Iron-CatalyzedReductive Ring-Rearrangement Reactionof Bridged Benzo[<i>b</i>]oxocin-4-ones with Grignard Reagentsto Afford Bridged Benzo[<i>b</i>]oxocin-2-ols

An iron-catalyzed reductive ring-rearrangement reaction of bridged benzo[<i>b</i>]oxocin-4-ones with Grignard reagents to produce bridged benzo[<i>b</i>]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.