Selective Rh(II)‐Catalyzed Intermolecular Oxyamidation and Acid‐Promoted Nucleophilic Cyclization Cascade of Enamides

In this work, we report an efficient and highly selective intermolecular Rh(II)‐catalyzed oxyamidation of enamides, affording valuable β‐amino piperidinone derivatives. The developed protocol demonstrates very high levels of chemo‐, regio‐, and diastereoselectivity across a broad substrate scope. The favored formation of the trans diastereomer provides compelling evidence for the transient involvement of an aziridine intermediate. Under acidic conditions, these intermediates subsequently undergo either nucleophilic cyclization or a Pictet–Spengler reaction, affording a broad array of novel 1‐amino‐izidine derivatives.