Copper-Catalyzed Hydroamination of Allenes: from Mechanistic Understanding to Methodology Development

Luca Alessandro Perego (1, 2) , Rémi Blieck (3) , Antoine Groué (4) , Florian Monnier (3) , Marc Taillefer (3) , Ilaria Ciofini (1) , Laurence Grimaud (2, 5)

1 IRCP - Institut de Recherche de Chimie Paris
2 PASTEUR - Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640)
3 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
4 PASTEUR - Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640)
5 LBM UMR 7203 - Laboratoire des biomolécules

Experimental and theoretical mechanistic studies on the Cu(OTf) 2-catalyzed hydroamination reaction of terminal allenes with secondary amines reveal that in-situ generated cationic Cu(I) is the catalytically active species and explain the observed regio-and stereoselectivity for the unbranched E product. Insight about the structure of the relevant transition states allowed the generalization of this methodology to allenamides and N-allenylcarbamates under unprecedentedly mild and functional group tolerant conditions. Chelation effect by the amide oxygen in addition to electronic effects explain the high innate reactivity of this class of substrates.

Mots clés: hydroamination; copper; allenes; allenamides; mechanism

Domaines: Catalyse; Chimie organique

Luca Alessandro Perego, Rémi Blieck, Antoine Groué, Florian Monnier, Marc Taillefer, et al.. Copper-Catalyzed Hydroamination of Allenes: from Mechanistic Understanding to Methodology Development. ACS Catalysis, 2017, ⟨10.1021/acscatal.7b00911⟩. ⟨hal-01525692⟩