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Abstract:

Benzyl and 2-propyl 6-O-acetyl-3,4-dideoxy-α-D-glycero-hex-3-enopyranosid-2-uloses (2) and (3) were readily prepared by the tin(IV) chloride-promoted glycosylation of glycal (1). The enone system of (2) and (3) underwent a highly diastereoselective Michael addition of thiols (ethanethiol, propane-2-thiol, and benzenemethanethiol) to afford the sulfur-containing hexopyranosid-2-ulose derivatives (4a-c) and (5a-c) in good yields. Sodium borohydride reduction of the carbonyl functionalities of (4b,c) and (5b) led to the corresponding 3-deoxy-4-thiohexopyranosides having the D-xylo (6b), (6c), and (8b) or the D-lyxo (7b), (7c), and (8c) configuration. Standard acetylation of these compounds gave the corresponding per-O-acetyl derivatives (10b), (10c), and (12b) and (11b), (11c), and (13b), useful for confirming all the previous configurational assignments by means of their 1H and 13C nuclear magnetic resonance spectra. Furthermore the 2-ulose (5b) proved to be a key intermediate for the synthesis of C-2 branched-chain 4-thiopyranosides, such as (16). The latter was synthesized by a good yielding ammonium acetate-catalysed Knoevenagel-type condensation of malononitrile with (5b).

Registro:

Documento: Artículo
Título:Michael addition of thiols to sugar enones. Synthesis of 3-deoxy-4-thiohexopyranosid-2-uloses as key precursors of 3-deoxy- and C-2 branched-chain 4-thiosugars
Autor:Uhrig, M.L.; Varela, O.
Filiación:Departamento de Quimica Organica, Universidad de Buenos Aires, Pabellon II, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Palabras clave:Acetylation; Benzene; Carbon; Derivatives; Hydrogen; Nuclear magnetic resonance spectroscopy; Synthesis (chemical); Glycosylation; Sugar enones; Sugar (sucrose)
Año:2002
Volumen:55
Número:1-2
Página de inicio:155
Página de fin:160
Título revista:Australian Journal of Chemistry
Título revista abreviado:Aust. J. Chem.
ISSN:00049425
CODEN:AJCHA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00049425_v55_n1-2_p155_Uhrig

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Citas:

---------- APA ----------
Uhrig, M.L. & Varela, O. (2002) . Michael addition of thiols to sugar enones. Synthesis of 3-deoxy-4-thiohexopyranosid-2-uloses as key precursors of 3-deoxy- and C-2 branched-chain 4-thiosugars. Australian Journal of Chemistry, 55(1-2), 155-160.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00049425_v55_n1-2_p155_Uhrig [ ]
---------- CHICAGO ----------
Uhrig, M.L., Varela, O. "Michael addition of thiols to sugar enones. Synthesis of 3-deoxy-4-thiohexopyranosid-2-uloses as key precursors of 3-deoxy- and C-2 branched-chain 4-thiosugars" . Australian Journal of Chemistry 55, no. 1-2 (2002) : 155-160.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00049425_v55_n1-2_p155_Uhrig [ ]
---------- MLA ----------
Uhrig, M.L., Varela, O. "Michael addition of thiols to sugar enones. Synthesis of 3-deoxy-4-thiohexopyranosid-2-uloses as key precursors of 3-deoxy- and C-2 branched-chain 4-thiosugars" . Australian Journal of Chemistry, vol. 55, no. 1-2, 2002, pp. 155-160.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00049425_v55_n1-2_p155_Uhrig [ ]
---------- VANCOUVER ----------
Uhrig, M.L., Varela, O. Michael addition of thiols to sugar enones. Synthesis of 3-deoxy-4-thiohexopyranosid-2-uloses as key precursors of 3-deoxy- and C-2 branched-chain 4-thiosugars. Aust. J. Chem. 2002;55(1-2):155-160.
Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00049425_v55_n1-2_p155_Uhrig [ ]