Reductive <i>ortho</i>-cyanomethylation of aryl iodanes with MeCN <i>via</i> one-pot iodonium-Claisen rearrangement

We report here a one-pot iodonium-Claisen rearrangement of aryl iodanes with acetonitrile, which enables <i>ortho</i>-cyanomethylation of aryl iodanes to produce valuable arylacetonitriles. The reaction proceeds through <i>in situ</i> preparation of (trimethylsilyl) acetonitrile by treating the readily available solvent MeCN with TMSOTf and DIPEA, followed by its interaction with aryl iodanes. Notably, the sequential use of two electrophilic reagents (TMSOTf and BF₃·Et₂O) to activate aryl iodanes is critical for driving the rearrangement.