I2‐Mediated Oxidative Amidation of Aryl Methyl Ketones: Synthesis of Primary α‐Ketoamides Using Ammonium Carbamodithioate as Amine Surrogate

Here we report the preparation of primary α‐ketoamides via a highly efficient molecular iodine‐mediated oxidative amidation of aryl methyl ketones with ammonium carbamodithioate. A self‐sequenced iodination/nucleophilic substitution/Kornblum oxidation/amidation mechanism was proposed. In this mechanism, α‐thiocyanatoacetophenone is the key intermediate. An I2‐mediated oxidative amidation leads to a wide variety of primary α‐ketoamides from aryl methyl ketones with ammonium carbamodithioate is described. Control experiments indicated an iodination/nucleophilic substitution/Kornblum oxidation/amidation mechanism.