Synthesis of Complex ortho‐Allyliodoarenes by Employing the Reductive Iodonio‐Claisen Rearrangement

I(o)dide behind the wheel: Aromatic hypervalent iodine(III) compounds reacted with allyltrimethylsilane in the presence of a Lewis acid to give ortho-allyliodoarenes through a reductive iodonio-Claisen rearrangement (see scheme). An meta-electron-donating group in the λ3-iodanes was indispensable to favor the [3,3]-sigmatropic rearrangement over reductive elimination. The method was successfully used for the concise synthesis of an antifungal natural product, broussin.