Ligand-Controlled Regiodivergent Hydroformylation of Ynamides: A Stereospecific and Regioselective Access to 2- and 3‑Aminoacroleins

The rhodium-catalyzed hydroformylation of ynamides is described and gives selective access to 2- or 3-aminoacrolein derivatives. The regioselectivity of this carbonylation can be completely controlled at will thanks to the nature of the ligand used. This represents the first example of regiodivergent alkyne hydroformylation. The influence of the substituents on the different positions of the ynamide has been investigated, and it appears that this reaction is tolerant to a wide range of functional groups.