Primary Amination of Enones Using Inorganic Ammonium Salts and Nitrogen Isotope Incorporation

Developing efficient methods to incorporate a primary amino group onto small molecules is of great importance in pharmaceutical and agrochemical fields. This significance becomes even more pronounced when it comes to accessing their corresponding 15 N isotopologs. Here, we present a mild, transition‐metal‐free, and stoichiometric oxidant‐free amination protocol for fluoroenones by employing user‐friendly ammonium carbonate as the primary amino source. The protocol demonstrates high atom economy by directly converting starting materials into the α ‐aminoenones. When the ammonia surrogate is replaced with a readily available combination of 15 NH 4 Cl and Na 2 CO 3 , a variety of completely 15 N‐labeled primary α ‐aminoenones can be synthesized with excellent functional group compatibility. The critical role of iodine in enhancing primary amination of fluoroenones is revealed by the transient formation of a more reactive iodinated enone, which facilitates downstream nucleophilic amination. Furthermore, the protocol exhibits robust scalability and is compatible with biologically and naturally relevant molecules. Molecular iodine is demonstrated as an inexpensive, environmentally benign, and easy‐to‐handle additive to pursue primary amination.