Ring-Opening Reactions of Aziridines Fused to a Conformationally Locked Tetrahydropyran Ring

• Published in: European Journal of Organic Chemistry 2009-12, Vol.2009 (36), p.6399-6406
• Main Authors: Karban, Jindřich, Kroutil, Jiří, Buděšínský, Miloš, Sýkora, Jan, Císařová, Ivana
• Format: Article
• Language: English
• Subjects: Aziridines; Carbohydrates; Carbohydrates with 4, 5, 6, ... C atoms, dissacharides and oligosaccharides; Carbohydrates. Nucleosides and nucleotides; Chemistry; Cleavage reactions; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Nitrogen heterocycles; Organic chemistry; Preparations and properties; Regioselectivity
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200900762

1,6‐Anhydro‐2,3,4‐trideoxy‐2,3‐(tosylepimino)‐β‐D‐hexopyranoses 1 and 2 underwent aziridine ring‐opening reactions with halides and other heteroatom‐centered nucleophiles. Ribo‐epimine 1 provided trans‐diaxial and cis products. The lyxo‐epimine 2 gave trans‐diaxial and trans‐diequatorial products, depending upon the reaction conditions (acid cleavage versus base cleavage) and the nucleophile (hard nucleophiles versus soft ones). These results have been rationalized by assuming that both SN2 and borderline SN2 cleavage mechanisms are operative. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) The ring‐opening reactions of aziridine derivatives of 1,6‐anhydro‐2,3,4‐trideoxy‐2,3‐(tosylepimino)‐β‐D‐hexopyranoses with nucleophiles [azide, halides, haloacids, benzylamine, benzyl alcohol and benzyl mercaptan (BnSH)] were studied, and the regioselectivity and stereoselectivity of the cleavage with respect to the Fürst–Plattner rule were examined.