Synthesis of chiral spiroacetals from carbohydrates

Synthesis of chiral spiroacetals from carbohydrates

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8 pages, 1 table, 7 schemes.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jo960060g

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Main Authors: Martín, Ángeles, Salazar, José A., Suárez, Ernesto
Other Authors: Ministerio de Educación y Ciencia (España)
Format: artículo biblioteca
Language:English
Published: American Chemical Society 1996-06-14
Online Access:http://hdl.handle.net/10261/17006
http://dx.doi.org/10.13039/501100008737
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spelling dig-ipna-es-10261-170062019-11-18T08:26:56Z Synthesis of chiral spiroacetals from carbohydrates Martín, Ángeles Salazar, José A. Suárez, Ernesto Ministerio de Educación y Ciencia (España) Dirección General de Investigación Científica y Técnica, DGICT (España) Gobierno de Canarias 8 pages, 1 table, 7 schemes.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jo960060g Chiral spiroacetals of the 1,7-dioxaspiro[5.5]undecane, 1,6-dioxaspiro[4.5]decane, and 1,6-dioxaspiro[4.4]nonane types have been prepared from carbohydrates in pyranose or furanose forms. The spirocyclization reaction has been accomplished from a conveniently homologated carbohydrate by an intramolecular hydrogen abstraction reaction promoted by alkoxy radicals. Thus, 2,3,4,6-tetra-O-benzyl-1-deoxy-1-(3'-hydroxypropyl)-α-d-glucopyranose (2) was photolyzed with visible light in the presence of (diacetoxyiodo)benzene and iodine to give a mixture of (1R)-(3) and (1S)-2,3,4,6-tetra-O-benzyl-1-deoxy-d-glucopyranose-1-spiro-2'-tetrahydrofuran (4). The photolysis of methyl 6-deoxy-6-(2'-hydroxyethyl)-2,3,4-tri-O-methyl-α-d-glucopyranoside (8) gave the isomeric spiroacetals methyl (5S)- (9) and (5R)-6-deoxy-5,2'-epoxy-6-ethyl-2,3,4-tri-O-methyl-α-d-glucopyranoside (10) in which the spirocenter is now located at C-5. The spiroacetals of the [5.5]undecane series: methyl (5R)- (19) and (5S)-6-deoxy-5,3'-epoxy-2,3,4-tri-O-methyl-6-propyl-β-d-glucopyranoside (20) have been prepared starting from methyl 6-deoxy-6-(3'-hydroxypropyl)-2,3,4-tri-O-methyl-β-d-glucopyranoside (18). The reaction has also been applied to hexofuranoses and 1-deoxy-1-(3'-hydroxypropyl)-2,3:5,6-di-O-isopropylidene-α-d-mannofuranose (21) gave rise to (1S)- (22) and (1R)-1-deoxy-2,3:5,6-di-O-isopropylidene-d-mannofuranose-1-spiro-2'-tetrahydrofuran (23); and 1-deoxy-1-(4'-hydroxybutyl)-2,3:5,6-di-O-isopropylidene-α-d-mannofuranose (28) to (1R)- (30) and (1S)-1-deoxy-2,3:5,6-di-O-isopropylidene-d-mannofuranose-1-spiro-2'-tetrahydropyran (32). Both spiroacetal enantiomers are formally available from the same carbohydrate. This work was supported by the Investigation Programme no. PB93-0171 of the Dirección General de Investigación Científica y Técnica and Programmes no. 93/030 and 93/014 of the Dirección General de Universidades e Investigación del Gobierno de Canarias. A.M. thanks the Ministerio de Educación y Ciencia, Spain, for a fellowship. Peer reviewed 2009-09-16T14:30:12Z 2009-09-16T14:30:12Z 1996-06-14 artículo http://purl.org/coar/resource_type/c_6501 Journal of Organic Chemistry 61(12): 3999-4006 (1996) 0022-3263 http://hdl.handle.net/10261/17006 10.1021/jo960060g http://dx.doi.org/10.13039/501100008737 en http://dx.doi.org/10.1021/jo960060g none 918459 bytes application/pdf American Chemical Society
institution IPNA ES
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country España
countrycode ES
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databasecode dig-ipna-es
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libraryname Biblioteca del IPNA España
language English
description 8 pages, 1 table, 7 schemes.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jo960060g
author2 Ministerio de Educación y Ciencia (España)
author_facet Ministerio de Educación y Ciencia (España)
Martín, Ángeles
Salazar, José A.
Suárez, Ernesto
format artículo
author Martín, Ángeles
Salazar, José A.
Suárez, Ernesto
spellingShingle Martín, Ángeles
Salazar, José A.
Suárez, Ernesto
Synthesis of chiral spiroacetals from carbohydrates
author_sort Martín, Ángeles
title Synthesis of chiral spiroacetals from carbohydrates
title_short Synthesis of chiral spiroacetals from carbohydrates
title_full Synthesis of chiral spiroacetals from carbohydrates
title_fullStr Synthesis of chiral spiroacetals from carbohydrates
title_full_unstemmed Synthesis of chiral spiroacetals from carbohydrates
title_sort synthesis of chiral spiroacetals from carbohydrates
publisher American Chemical Society
publishDate 1996-06-14
url http://hdl.handle.net/10261/17006
http://dx.doi.org/10.13039/501100008737
work_keys_str_mv AT martinangeles synthesisofchiralspiroacetalsfromcarbohydrates
AT salazarjosea synthesisofchiralspiroacetalsfromcarbohydrates
AT suarezernesto synthesisofchiralspiroacetalsfromcarbohydrates
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