Straightforward access to cyclic amines by dinitriles reduction

Stéphane Laval (1) , Wissam Dayoub (1) , Leyla Pehlivan (1) , Estelle Métay (2) , Alain Favre-Reguillon (3, 1) , Dominique Delbrayelle (4) , Gérard Mignani (5) , Marc Lemaire (2)

1 ICBMS - Institut de Chimie et Biochimie Moléculaires et Supramoléculaires
2 CASYEN - Catalyse Synthèse et Environnement
3 LTCP - Laboratoire de transformations chimiques et pharmaceutiques
4 MINAKEM SAS, 145 Chemin des Lilas, 59310 Beuvry la Foret, France -
5 Rhodia Centre de Recherche

1,1,3,3-Tetramethyldisiloxane (TMDS) and polymethylhydrosiloxane (PMHS), when associated with titanium(IV) isopropoxide, provide two convenient systems for the reduction of nitriles into the corresponding primary amines. Kinetics of the two systems have been studied by 1H NMR and demonstrated that reduction with PMHS occurs faster than with TMDS. These two titanium-based systems reduce both aromatic and aliphatic nitriles in the presence of Br, Cdouble bond; length as m-dashC, NO2, OH, and cyclopropyl-ring. In the case of cyclopropyl-nitriles, the formation of secondary amines, which come from an intermolecular reductive alkylation reaction was observed. This result was exploited for the reduction of dinitriles, which led, in one-step, to azepane, piperidine, pyrrolidine, and azetidine derivatives through an intramolecular reductive alkylation reaction.

Mots clés: Reduction; Nitriles; Hydrosiloxanes; Titanium; Amines

Domaines: Chimie organique

Stéphane Laval, Wissam Dayoub, Leyla Pehlivan, Estelle Métay, Alain Favre-Reguillon, et al.. Straightforward access to cyclic amines by dinitriles reduction. Tetrahedron, 2014, 70 (4), pp.975-983. ⟨hal-01179511⟩