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Stereoselective synthesis of 2-deoxy-2-iodo-glycosides from furanoses. A new route to 2-deoxy-glycosides and 2-deoxy-oligosaccharides of ribo and xylo configuration.
J Org Chem. 2005 Dec 09; 70(25):10297-310.JO

Abstract

[reaction: see text] A general procedure for the stereoselective synthesis of 2-deoxy-2-iodo-hexo- and -hepto-pyranosyl glycosides from furanoses is reported. The proposed methodology provides a new route for accessing 2-deoxy-oligosaccharides. The procedure involves three reactions: Wittig-Horner olefination to give alkenyl sulfanyl derivatives, electrophilic iodine-induced cyclization to give phenyl 2-deoxy-2-iodo-1-thio-hexo-glycosides, and glycosylation. Protected furanoses 1, 3, and 6-11, which include examples of the four possible isomeric configurations of furanoses, were reacted with diphenyl phenylsulfanylmethyl phosphine oxide to give the alkenyl sulfanyl derivatives 2, 4, and 12-16. The iodine-induced cyclization of these compounds afforded the phenyl 2-deoxy-2-iodo-1-thio-glycosides 18, 20, and 22-27 with practically complete regio- and stereoselectivity. Products of 6-endo cyclization, in which the iodine at C-2 was in a cis relationship with the alkoxy at C-3, were almost exclusively produced. Better yields were obtained for compounds with a ribo or xylo configuration than for compounds with other configurations. Compounds 18, 20, and 22-27 were found to be efficient glycosyl donors in the glycosylation of cholesterol and glucopyranoside 29a, affording the corresponding 2-deoxy-2-iodo-glycosides and 2-deoxy-2-iodo-oligosaccharides with good yields and stereoselectivities. The glycosydic bond in the major isomers was always trans to the iodine at C-2.

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Authors+Show Affiliations

Rodríguez MA
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virigili, C/ Marcel-lí Domingo s/n, 43007 Tarragona, Spain.
Boutureira O
No affiliation info available
Arnés X
No affiliation info available
Matheu MI
No affiliation info available
Díaz Y
No affiliation info available
Castillón S
No affiliation info available

MeSH

Deoxy SugarsFuransGlycosidesGlycosylationOligosaccharidesStereoisomerism

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

16323838

Citation

Rodríguez, Miguel Angel, et al. "Stereoselective Synthesis of 2-deoxy-2-iodo-glycosides From Furanoses. a New Route to 2-deoxy-glycosides and 2-deoxy-oligosaccharides of Ribo and Xylo Configuration." The Journal of Organic Chemistry, vol. 70, no. 25, 2005, pp. 10297-310.
Rodríguez MA, Boutureira O, Arnés X, et al. Stereoselective synthesis of 2-deoxy-2-iodo-glycosides from furanoses. A new route to 2-deoxy-glycosides and 2-deoxy-oligosaccharides of ribo and xylo configuration. J Org Chem. 2005;70(25):10297-310.
Rodríguez, M. A., Boutureira, O., Arnés, X., Matheu, M. I., Díaz, Y., & Castillón, S. (2005). Stereoselective synthesis of 2-deoxy-2-iodo-glycosides from furanoses. A new route to 2-deoxy-glycosides and 2-deoxy-oligosaccharides of ribo and xylo configuration. The Journal of Organic Chemistry, 70(25), 10297-310.
Rodríguez MA, et al. Stereoselective Synthesis of 2-deoxy-2-iodo-glycosides From Furanoses. a New Route to 2-deoxy-glycosides and 2-deoxy-oligosaccharides of Ribo and Xylo Configuration. J Org Chem. 2005 Dec 9;70(25):10297-310. PubMed PMID: 16323838.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Stereoselective synthesis of 2-deoxy-2-iodo-glycosides from furanoses. A new route to 2-deoxy-glycosides and 2-deoxy-oligosaccharides of ribo and xylo configuration. AU - Rodríguez,Miguel Angel, AU - Boutureira,Omar, AU - Arnés,Xavier, AU - Matheu,M Isabel, AU - Díaz,Yolanda, AU - Castillón,Sergio, PY - 2005/12/6/pubmed PY - 2006/6/15/medline PY - 2005/12/6/entrez SP - 10297 EP - 310 JF - The Journal of organic chemistry JO - J. Org. Chem. VL - 70 IS - 25 N2 - [reaction: see text] A general procedure for the stereoselective synthesis of 2-deoxy-2-iodo-hexo- and -hepto-pyranosyl glycosides from furanoses is reported. The proposed methodology provides a new route for accessing 2-deoxy-oligosaccharides. The procedure involves three reactions: Wittig-Horner olefination to give alkenyl sulfanyl derivatives, electrophilic iodine-induced cyclization to give phenyl 2-deoxy-2-iodo-1-thio-hexo-glycosides, and glycosylation. Protected furanoses 1, 3, and 6-11, which include examples of the four possible isomeric configurations of furanoses, were reacted with diphenyl phenylsulfanylmethyl phosphine oxide to give the alkenyl sulfanyl derivatives 2, 4, and 12-16. The iodine-induced cyclization of these compounds afforded the phenyl 2-deoxy-2-iodo-1-thio-glycosides 18, 20, and 22-27 with practically complete regio- and stereoselectivity. Products of 6-endo cyclization, in which the iodine at C-2 was in a cis relationship with the alkoxy at C-3, were almost exclusively produced. Better yields were obtained for compounds with a ribo or xylo configuration than for compounds with other configurations. Compounds 18, 20, and 22-27 were found to be efficient glycosyl donors in the glycosylation of cholesterol and glucopyranoside 29a, affording the corresponding 2-deoxy-2-iodo-glycosides and 2-deoxy-2-iodo-oligosaccharides with good yields and stereoselectivities. The glycosydic bond in the major isomers was always trans to the iodine at C-2. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/16323838/Stereoselective_synthesis_of_2_deoxy_2_iodo_glycosides_from_furanoses__A_new_route_to_2_deoxy_glycosides_and_2_deoxy_oligosaccharides_of_ribo_and_xylo_configuration_ L2 - https://dx.doi.org/10.1021/jo051461b DB - PRIME DP - Unbound Medicine ER -