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Abstract:

The synthesis of 4-thio-D-galactofuranose (15) and derivatives, starting from methyl α-D-glucopyranoside (1), is described. Esterification of 1 with N-benzoylimidazole afforded regioselectively methyl 2,3,6-tri-O-benzoyl-α-D-glucopyranoside (2c). Further sulfonylation of HO-4 of 2c gave methyl 2,3,6-tri-0-benzoyl-4-0-(p-tolyl-sulfonyl)-α-D-glucopyranoside (2e) or methyl 2,3,6-tri-0-benzoyl-4-0-[(p-bromophenyl)sulfonyl]-α-D-glucopyranoside (2f). Nucleophilic substitution of the sulfonyloxy group by thiocyanate led to methyl 2,3,6-tri-0-benzoyl-4-deoxy-4-thiocyano-α-D-galactopyranoside (3). This reaction allowed the simultaneous introduction of a group precursor of thiol and the inversion of the configuration at C-4. Compound 3 was reduced to methyl 4-5-acetyl-2,3,6-tri-0-benzoyl-4-thio-α-D-galactopyranoside (4a) or methyl 2,3,6-tri-0-benzoyl-4-thio-α-D-galacto-pyranoside (4b). The latter was debenzoylated to give methyl 4-thio-α-D-galactopyranoside (5). This product was also obtained by alkaline methanolysis of 3. Ring contraction was achieved by acetolysis of 5, which produced l,2,3,5,6-penta-0-acetyl-4-thio-α-D-galactofuranose (10) and its β-anomer (11) as the main products. The product distribution in the acetolysis reaction of 4-thiopyranose derivatives would depend on the stability of the ionic intermediates involved. O-Deacetylation of 10 led to 4-thio-D-galactofuranose (15). © 1989, American Chemical Society. All rights reserved.

Registro:

Documento: Artículo
Título:A Convenient Synthesis of 4-Thio-D-galactofuranose
Autor:Varela, O.; Cicero, D.; De Lederkremer, R.M.
Filiación:Departamento de Química Orgánica, Facultad de Ciencias Exactas Y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428, Buenos Aires, Argentina
Año:1989
Volumen:54
Número:8
Página de inicio:1884
Página de fin:1890
DOI: http://dx.doi.org/10.1021/jo00269a025
Título revista:Journal of Organic Chemistry
Título revista abreviado:J. Org. Chem.
ISSN:00223263
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v54_n8_p1884_Varela

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Citas:

---------- APA ----------
Varela, O., Cicero, D. & De Lederkremer, R.M. (1989) . A Convenient Synthesis of 4-Thio-D-galactofuranose. Journal of Organic Chemistry, 54(8), 1884-1890.
http://dx.doi.org/10.1021/jo00269a025
---------- CHICAGO ----------
Varela, O., Cicero, D., De Lederkremer, R.M. "A Convenient Synthesis of 4-Thio-D-galactofuranose" . Journal of Organic Chemistry 54, no. 8 (1989) : 1884-1890.
http://dx.doi.org/10.1021/jo00269a025
---------- MLA ----------
Varela, O., Cicero, D., De Lederkremer, R.M. "A Convenient Synthesis of 4-Thio-D-galactofuranose" . Journal of Organic Chemistry, vol. 54, no. 8, 1989, pp. 1884-1890.
http://dx.doi.org/10.1021/jo00269a025
---------- VANCOUVER ----------
Varela, O., Cicero, D., De Lederkremer, R.M. A Convenient Synthesis of 4-Thio-D-galactofuranose. J. Org. Chem. 1989;54(8):1884-1890.
http://dx.doi.org/10.1021/jo00269a025