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

  • Datos identificativos

    Identificador: PC:1156
    Autores:
    M. Isabel MatheuAndrea KövérOmar BoutureiraYolanda DíazSergio Castillón
    Resumen:
    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.
  • Otros:

    Autor según el artículo: M. Isabel Matheu Andrea Kövér Omar Boutureira Yolanda Díaz Sergio Castillón
    Departamento: Química Analítica i Química Orgànica
    Autor/es de la URV: MATHEU MALPARTIDA, MARÍA ISABEL Andrea Kövér Omar Boutureira Yolanda Díaz Sergio Castillón
    Palabras clave: deoxycarbohydrates
    Resumen: 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.
    Grupo de investigación: Síntesis Orgànica Estereoselectiva
    Áreas temáticas: Química Química Chemistry
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0022-3263
    Identificador del autor: 0000-0001-5216-9260 n/a 0000-0002-0768-8309 0000-0001-5567-8108 n/a
    Fecha de alta del registro: 2015-04-16
    Página final: 3068
    Volumen de revista: 79
    Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
    Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/jo5001912
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI del artículo: 10.1021/jo5001912
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2014
    Página inicial: 3060
    Tipo de publicación: Article Artículo Article
  • Palabras clave:

    Esterificació
    Estereoquímica
    Carbohidrats
    deoxycarbohydrates
    Química
    Química
    Chemistry
    0022-3263
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