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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...
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