the first time by X‐ray structural analysis. The ortho‐methoxymethyl group and the carbonyl oxygen coordinate to the iodine atom of the iminoiodinane. Activation of the N‐acyliminoiodinane was achieved by photoirradiation at 370 nm, thereby enabling reaction with various silylenol ethers to give α‐aminoketone derivatives in good to high yield. N‐sulfonyliminoiodinanes bearing ortho substituents were