Transition Metal‐Free N−S Bond Cleavage and C−N Bond Activation of Ugi‐Adducts for Rapid Preparation of Primary Amides and α‐Ketoamides

<jats:title>Abstract</jats:title>A novel method of transition metal‐free N−S bond cleavage and subsequent C−N bond activation of Ugi‐adducts was developed. Diverse primary amides and α‐ketoamides were prepared in a rapid, step‐economical and highly efficient manner in two steps. This strategy features excellent chemoselectivity, high yield and functional‐group tolerance. Primary amides derived from the pharmaceuticals probenecid and febuxostat were prepared. This method opens a new pathway for the simultaneous synthesis of primary amides and α‐ketoamides in an environmentally friendly manner.