From Simple Cyclic 1,3-Ketoamides to Complex Spirolactams by Supported Heterogeneous Organocatalysis with PS-BEMP

Aouicha Benmaati , Hadjira Habib Zahmani , Salih Hacini , José Carlos Menéndez (1) , Xavier Bugaut (2) , Jean Rodriguez (2) , Thierry Constantieux (2)

1 UCM - Universidad Complutense de Madrid = Complutense University of Madrid [Madrid]
2 ISM2 - Institut des Sciences Moléculaires de Marseille

The reaction between cyclic 1,3-ketoamides and Michael acceptors in the presence of a catalytic amount of a polymer-supported organobase PS-BEMP has been developed for a direct access to spirocyclic 1,3-ketolactams through a domino Michael addition/hemiacetalization sequence. The products could be isolated in high chemical yields and purities after simple filtration, and the catalyst could be re-used without any re-activation. These spirolactams, containing a hemiaminal moiety, may be viewed as precursors of N-acyliminium intermediates upon Lewis acid activation, which allowed various subsequent functionalizations leading to original polycyclic lactams.

Mots clés: supported organobase; Michael addition; spirolactam; heterogeneous organocatalysis; N-acyliminium intermediate

Domaines: Chimie organique

Aouicha Benmaati, Hadjira Habib Zahmani, Salih Hacini, José Carlos Menéndez, Xavier Bugaut, et al.. From Simple Cyclic 1,3-Ketoamides to Complex Spirolactams by Supported Heterogeneous Organocatalysis with PS-BEMP. Synthesis: Journal of Synthetic Organic Chemistry, 2016, 48 (19), pp.3217 - 3231. ⟨10.1055/s-0035-1561485⟩. ⟨hal-01415069⟩