Ring opening of benzyl β-D-galactoside cyclic sulfates into galactose monosulfates. New access to 6-deoxy-galacto-hex-5-enopyranoside and 4-deoxy-3-ketogalactopyranoside

Article abstract of DOI:10.1080/07328300008544080

The behavior of 3,4- and 4,6-cyclic sulfates derived from benzyl 2,6- and 2,3-di-O-benzyl-β-D-galactopyranosides toward hydrolysis has been studied using aqueous sodium hydroxide under various conditions. Starting from benzyl 2,6-di-O-benzyl-3,4-O-sulfuryl-β-D-galactopyranoside (5), the reaction with aq NaOH in THF gave both 3- and 4-monosulfates 7 and 8 (83%, in 68:32 ratio), while the reaction in DMF led unexpectedly to the 4-deoxy-3-keto derivative 10 in 77% yield after acidic hydrolysis of the intermediate enolester 9. On the other hand, when benzyl 2,3-di-O-benzyl-4,6-O-sulfuryl-β-D-galactopyranoside (6) was treated with aq NaOH in THF, a mixture of benzyl 2,3-di-O-benzyl-6-deoxy-4-O-(sodium sulfonato)-α-L-arabino-hex-5-enopyranoside (11) and benzyl 2,3-di-O-benzyl-4-deoxy-6-O-(sodium sulfonato)-α-L-threo-hex-4-enopyranoside (12) (in 65:35 ratio) was obtained in 93% yield, giving a new and rapid access to 11, a potential precursor of L-sugars derivatives. Alternatively, BzONBu₄ gave a regiospecific opening reaction of 6 and led to the 6-O-benzoate 4-O-sulfate derivative (13) in excellent yield.

Full text of DOI:10.1080/07328300008544080

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Ring Opening of Benzyl β-D-
Galactoside Cyclic Sulfates into
Galactose Monosulfates. New
Access to 6-Deoxy-Galacto-Hex-5-
Enopyranoside and 4-Deoxy-3-
Ketogalactopyranoside.
Franck Dagron & André Lubineau
a Laboratoire de Chimie Organique Multifonctionnelle, UMR
CNRS 8614, Institut de Chimie Moléculaire d'Orsay, Université
Paris-Sud , Bât. 420, 91405 Orsay Cedex, France
b Laboratoire de Chimie Organique Multifonctionnelle, UMR
CNRS 8614, Institut de Chimie Moléculaire d'Orsay, Université
Paris-Sud , Bât. 420, 91405 Orsay Cedex, France
Published online: 27 Feb 2008.
To cite this article: Franck Dagron & André Lubineau (2000) Ring Opening of Benzyl β-D-
Galactoside Cyclic Sulfates into Galactose Monosulfates. New Access to 6-Deoxy-Galacto-
Hex-5-Enopyranoside and 4-Deoxy-3-Ketogalactopyranoside., Journal of Carbohydrate
Chemistry, 19:3, 311-321, DOI: 10.1080/07328300008544080
To link to this article: http://dx.doi.org/10.1080/07328300008544080
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