Nickel-Catalyzed Hydroamination and Hydroalkoxylation of Enelactams with Unactivated Amines and Alcohols

Nickel-catalyzed hydroamination and hydroalkoxylation of enelactams with unactivated amines and alcohols are reported. This method showed good functional group tolerance and delivered the corresponding hydrofunctionalized products in good to excellent yields (≤98%). Furthermore, an intramolecular hydroalkoxylation of an enelactam was also realized, giving a cyclization product in a good yield. Mechanistic studies indicated that tBuI acts as a hydride donor and radical precursor, which is crucial for the success of the reaction.