Fe-promoted cross coupling of homobenzylic methyl ethers with Grignard reagents via sp3 C–O bond cleavage

The first iron-catalyzed formal cross coupling of homobenzylic methyl ethers with alkyl Grignard reagents is realized. The reaction is proposed to proceed through a sequence of dehydroalkoxylation to form the vinyl-intermediate, followed by Fe-catalyzed selective carbometalation to form a benzylic Grignard reagent.