Hypervalent Iodine Reagent-Promoted Hofmann-Type Rearrangement/Carboxylation of Primary Amides

A novel transformation of primary amides to secondary amides promoted by hypervalent iodine reagents was developed. The hypervalent iodine reagent-mediated Hofmann-type rearrangement generated an isocyanate intermediate, which was subsequently trapped by an in situ generated carboxylic acid from the hypervalent iodine reagent to provide the corresponding secondary amides. This method provided a facile and efficient route for the synthesis of secondary amides from primary amides and also revealed novel reactivities of hypervalent iodine reagents.