Intermolecular Rhodium(II)-Catalyzed Allylic C(sp 3)-H Amination of Cyclic Enamides

Romain Rey-Rodriguez (1) , Grégory Jestin , Vincent Gandon (2) , Gwendal Grelier (3) , Pascal Retailleau (3) , Benjamin Darses (3) , Philippe Dauban (3) , Isabelle Gillaizeau (1)

1 ICOA - Institut de Chimie Organique et Analytique
2 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay
3 ICSN - Institut de Chimie des Substances Naturelles

The intermolecular rhodium(II)-catalyzed C(sp 3)-H amination of enamides gives access to new 4-aminopiperidine derivatives that are useful building blocks in medicinal chemistry. This efficient transformation proceeds at room temperature with complete regio- and chemoselectivity in favor of the allylic C(sp 3)-H bond, and has a broad functional group tolerance. In addition, the matched combination of the chiral complex Rh2(S-nta)4 [nta = (S)-N-1,8-naphthoylalanine] with an optically pure (S)-sulfonimidamide allows the isolation of allylic amines with excellent stereocontrol.

Mots clés: rhodium catalysis; heterocycles; enamides; allylic amination; nitrenes

Domaines: Chimie organique; Catalyse

Romain Rey-Rodriguez, Grégory Jestin, Vincent Gandon, Gwendal Grelier, Pascal Retailleau, et al.. Intermolecular Rhodium(II)-Catalyzed Allylic C(sp 3)-H Amination of Cyclic Enamides. Advanced Synthesis and Catalysis, 2018, 360 (3), pp.513-518. ⟨10.1002/adsc.201701188⟩. ⟨hal-02366212⟩