The Reactivity of Enantiopure (S)-6-Oxopipecolic Acid and Corresponding Pyridoisoquinolines Under Acidic Conditions

Peter Šafář (1) , Štefan Marchalín (2, 1, 3) , Barbora Balónová (4) , Michal Šoral (1) , Ján Moncol (1) , Alina Ghinet (5, 6, 7, 8) , Benoît Rigo (5, 7) , Adam Daïch (2, 1, 3)

1 STU - Slovak University of Technology in Bratislava
2 URCOM - Unité de Recherche en Chimie Organique et Macromoléculaire
3 INC3M - Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire
4 University of Kent [Canterbury]
5 LIRIC - Lille Inflammation Research International Center - U 995
6 UAIC - Alexandru Ioan Cuza University of Iași = Universitatea Alexandru Ioan Cuza din Iași
7 HEI - Hautes Etudes d’Ingénieur [Lille]
8 RID-AGE - Facteurs de Risque et Déterminants Moléculaires des Maladies liées au Vieillissement - U 1167

Enantiopure N-benzyl 6-oxopipecolic acid, obtained from (S)-2-aminoadipic acid, was evaluated under π-cationic cyclization conditions. If the combination of SOCl2/AlCl3 seems to be superior in terms of the reaction yields, use of PPA, (CF3CO)2O/BF3·Et2O, and Eaton's reagent is also very interesting since in addition to the expected keto-lactam, reduced- and oxidized keto-lactam, enamides and enamidones containing CF3CO– residue are isolated. Mechanisms leading to these products as well as the ones resulting from their acidic treatment were proposed and discussed with the help, in some cases, of univocal transformations and X-ray analysis.

Mots clés: Nitrogen heterocycles; Polycycles; Amino acids; Cyclization; N-Acyliminium Species; Nitrogen heterocycles

Domaines: Chimie

Peter Šafář, Štefan Marchalín, Barbora Balónová, Michal Šoral, Ján Moncol, et al.. The Reactivity of Enantiopure (S)-6-Oxopipecolic Acid and Corresponding Pyridoisoquinolines Under Acidic Conditions. European Journal of Organic Chemistry, 2018, 2018 (40), pp.5499-5511. ⟨10.1002/ejoc.201800908⟩. ⟨hal-02413282⟩