Palladium‐Catalyzed Silylcyanation of Ynamides: Regio‐ and Stereoselective Access to Tetrasubstituted 3‐Silyl‐2‐Aminoacrylonitriles

Pierre Hansjacob (1) , Frédéric R. Leroux (1) , Vincent Gandon (2, 3) , Morgan Donnard (1)

1 LIMA - Laboratoire d'innovation moléculaire et applications
2 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay
3 LCM - Laboratoire de chimie moléculaire

The palladium-catalyzed silylcyanation of ynamides is described. This reaction is fully regioselective, delivering tetrasubstituted 2-aminoacrylonitriles derivatives exclusively. Unexpectedly, the nature (aryl or alkyl) of the substituent located at the β-position of the ynamide directly controls the stereoselectivity. The reaction tolerates a number of functional groups and can be considered as the first general access to fully substituted 2-aminoacrylonitriles. Given the singular reactivity observed, a computational study was performed to shed light on the mechanism of this intriguing transformation. Relying on the specific reactivity of the newly installed vinylsilane functionality, the scope of 2-aminoacrylonitriles has been enlarged by postfunctionalization.

Domaines: Chimie organique; Catalyse

Pierre Hansjacob, Frédéric R. Leroux, Vincent Gandon, Morgan Donnard. Palladium‐Catalyzed Silylcyanation of Ynamides: Regio‐ and Stereoselective Access to Tetrasubstituted 3‐Silyl‐2‐Aminoacrylonitriles. Angewandte Chemie International Edition, 2022, ⟨10.1002/anie.202200204⟩. ⟨hal-03541070⟩