We discovered a highly reactive λ3-hypervalent iodane species using an inorganic/organic base for the unorthodox synthesis of amides and ketoesters through grafting terminal alkynes. In contrast to the metal-catalyzed dehydrative approaches the in situ generated nonmetallic reagent efficiently created C-N/C-O and CO bonds with amines/alkynes and water at rt. This journal is © The Royal Society of Chemistry 2015.