Aldehydes as CO Releasing Molecules: <i>In Situ</i> and <i>Ex Situ</i> Giese Reactions and Palladium-Catalyzed Aminocarbonylations

We report the adoption of a two-chamber reactor making use of aliphatic aldehydes in the role of CO releasing molecules (CORMs). Upon photocatalytic conditions, an acyl radical (RCO^•) was first formed, prone to lose CO. The resulting alkyl radical was employed in the <i>in situ</i> conjugate addition onto a Michael acceptor (in the first chamber), and the released CO was employed in <i>ex situ</i> palladium-catalyzed aminocarbonylations (in the second chamber) to ensure a 100% atom-economical reaction.