1,3,5-Oxadiazine Framework by Oxygen vs. Nitrogen Trapping of an N-Acyliminium Ion Derived from N,O-bis-TMS Pyroglutamic Acid

A. Ghinet (1, 2, 3) , C.-M. Abuhaie (1, 2, 3) , G. Homerin (1, 3) , H. Marzag (4) , J. Dubois (5) , E. Lipka (1, 6) , B. Rigo (1, 3) , Adam Daïch (4)

1 LIRIC - Lille Inflammation Research International Center - U 995
2 UAIC - Alexandru Ioan Cuza University of Iași = Universitatea Alexandru Ioan Cuza din Iași
3 HEI - Hautes Etudes d’Ingénieur [Lille]
4 URCOM - Unité de Recherche en Chimie Organique et Macromoléculaire
5 ICSN - Institut de Chimie des Substances Naturelles
6 Faculté de Médecine Henri Warembourg - Université de Lille

We report that the reaction of N,O-bis-TMS pyroglutamic acid with aldehydes, under basic or acid catalysis leads to O-bis-TMS adducts. Treatment of these N,O-acetals by TfOH affords azalactones or N,N′-substituted methylene-bis-pyroglutamic acids from the trapping of N-acyliminium species, respectively, with oxygen or nitrogen atom intramolecularly versus intermolecularly. Anodic oxidation of the amido acids, followed by diastereoselective oxa-cyclisation of new N-acyliminium salts, provides exclusively fused meso-1,3,5-oxadiazines with the stereochemistry secured by X-ray analysis. The reactivity of these skeletons under both alkaline and acid conditions was also envisioned and discussed. © 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim

Mots clés: O-Acetal; Bis-N; Pyroglutamic acid; Heterocyclisation; 1; 3; 5-Oxadiazine; N-Acyliminium

Domaines: Chimie

A. Ghinet, C.-M. Abuhaie, G. Homerin, H. Marzag, J. Dubois, et al.. 1,3,5-Oxadiazine Framework by Oxygen vs. Nitrogen Trapping of an N-Acyliminium Ion Derived from N,O-bis-TMS Pyroglutamic Acid. ChemistrySelect, 2017, 2 (33), pp.10654-10660. ⟨10.1002/slct.201701766⟩. ⟨hal-02413278⟩