Articles producció científica> Química Analítica i Química Orgànica

Tuning the Stereoelectronic Properties of 1-Sulfanylhex-1-enitols for the Sequential Stereoselective Synthesis of 2-Deoxy-2-iodo-ß-D-allopyranoside

  • Dades identificatives

    Identificador: PC:1156
    Autors:
    M. Isabel MatheuAndrea KövérOmar BoutureiraYolanda DíazSergio Castillón
    Resum:
    The preparation of challenging 2-deoxy-2-iodo-β-D-allo precursors of 2-deoxy-β-D-ribo-hexopyranosyl units and other analogues is reported using a robust olefination−cyclization−glycosylation sequence. Here, we particularly focus on tuning the stereoelectronic properties of the alkenyl sulfides intermediates in order to improve the diastereoselectivity of the cyclization step and, hence, the efficiency of the overall transformation. Phosphine oxides with the general formula Ph2P(O)CH2SR (R = t- Bu, Cy, p-MeOPh, 2,6-di-ClPh, and 2,6-di-MePh) were easily synthesized and subsequently used in the olefination reaction with 2,3,5-tri-O-benzyl-D-ribose and -D-arabinose. The corresponding sugar-derived alkenyl sulfides were submitted to a 6-endo [I+]- induced cyclization, and the resulting 2-deoxy 2-iodohexopyranosyl-1-thioglycosides were used as glycosyl donors for the stereoselective synthesis of 2-deoxy-2-iodohexopyranosyl glycosides. Among the different S-groups studied, t-Bu derivative was the best performer for the synthesis of cholesteryl 2-deoxy-2-iodomannopyranosides, whereas for the synthesis of 2-deoxy-2- iodoallopyranosides none of the derivatives here studied proved superior to the phenyl analogue previously described. Glycosylation of cholesterol with different D-allo and D-manno derivatives produced 2-deoxy-2-iodoglycosides with stereoselectivities in the same order in each case, reinforcing the involvement of an oxocarbenium ion as the common intermediate of this crucial glycosylation step.
  • Altres:

    Autor segons l'article: M. Isabel Matheu Andrea Kövér Omar Boutureira Yolanda Díaz Sergio Castillón
    Departament: Química Analítica i Química Orgànica
    Autor/s de la URV: MATHEU MALPARTIDA, MARÍA ISABEL Andrea Kövér Omar Boutureira Yolanda Díaz Sergio Castillón
    Paraules clau: deoxycarbohydrates
    Resum: The preparation of challenging 2-deoxy-2-iodo-β-D-allo precursors of 2-deoxy-β-D-ribo-hexopyranosyl units and other analogues is reported using a robust olefination−cyclization−glycosylation sequence. Here, we particularly focus on tuning the stereoelectronic properties of the alkenyl sulfides intermediates in order to improve the diastereoselectivity of the cyclization step and, hence, the efficiency of the overall transformation. Phosphine oxides with the general formula Ph2P(O)CH2SR (R = t- Bu, Cy, p-MeOPh, 2,6-di-ClPh, and 2,6-di-MePh) were easily synthesized and subsequently used in the olefination reaction with 2,3,5-tri-O-benzyl-D-ribose and -D-arabinose. The corresponding sugar-derived alkenyl sulfides were submitted to a 6-endo [I+]- induced cyclization, and the resulting 2-deoxy 2-iodohexopyranosyl-1-thioglycosides were used as glycosyl donors for the stereoselective synthesis of 2-deoxy-2-iodohexopyranosyl glycosides. Among the different S-groups studied, t-Bu derivative was the best performer for the synthesis of cholesteryl 2-deoxy-2-iodomannopyranosides, whereas for the synthesis of 2-deoxy-2- iodoallopyranosides none of the derivatives here studied proved superior to the phenyl analogue previously described. Glycosylation of cholesterol with different D-allo and D-manno derivatives produced 2-deoxy-2-iodoglycosides with stereoselectivities in the same order in each case, reinforcing the involvement of an oxocarbenium ion as the common intermediate of this crucial glycosylation step.
    Grup de recerca: Síntesis Orgànica Estereoselectiva
    Àrees temàtiques: Química Química Chemistry
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0022-3263
    Identificador de l'autor: 0000-0001-5216-9260 n/a 0000-0002-0768-8309 0000-0001-5567-8108 n/a
    Data d'alta del registre: 2015-04-16
    Pàgina final: 3068
    Volum de revista: 79
    Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
    Enllaç font original: https://pubs.acs.org/doi/10.1021/jo5001912
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI de l'article: 10.1021/jo5001912
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2014
    Pàgina inicial: 3060
    Tipus de publicació: Article Artículo Article
  • Paraules clau:

    Esterificació
    Estereoquímica
    Carbohidrats
    deoxycarbohydrates
    Química
    Química
    Chemistry
    0022-3263
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