Abstract:
A convenient synthesis of enantiomerically pure aldopentono-1,4-thiolactones is described. Thus, 4-thio-d-ribono-1,4-lactone (12) has been prepared from D-gulono-1,4-lactone (1), via its 2,3-O-isopropylidene derivative 3. The 5,6-glycol system of 3 was oxidized with NaIO4. Chemoselective reduction of the resulting aldehyde function with NaBH3CN led to 2,3-O-isopropylidene-l-lyxono-1,4-lactone (7). Tosylation of 7 and subsequent treatment of the tosylate 8 with sodium methoxide afforded methyl 4,5-epoxy-2,3-O-isopropylidene-l-lyxonate (9) as a key intermediate. Treatment of 9 with thiourea gave the 4,5-thiirane derivative having the d-ribo configuration (10). Regioselective opening of the thiirane ring and simultaneous thiolactonization took place by heating 10 with KOAc-HOAc-DMF. The resulting 5-O-acetyl-2,3-O-isopropylidene-4-thio-d-ribono-1,4-lactone (11) was readily converted, by acid removal (2% HCl) of the protecting groups, into the crystalline thiolactone 12. A similar approach was employed for the synthesis of 4-thio-l-lyxono-1,4-lactone (19), starting from d-ribono-1,4-lactone (13). © 1993, American Chemical Society. All rights reserved.
Registro:
Documento: |
Artículo
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Título: | First Synthesis of Aldopentono-1,4-thiolactones |
Autor: | Varela, O.; Zunszain, P.A. |
Filiación: | Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428, Buenos Aires, Argentina
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Año: | 1993
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Volumen: | 58
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Número: | 27
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Página de inicio: | 7860
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Página de fin: | 7864
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DOI: |
http://dx.doi.org/10.1021/jo00079a034 |
Título revista: | Journal of Organic Chemistry
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Título revista abreviado: | J. Org. Chem.
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ISSN: | 00223263
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v58_n27_p7860_Varela |
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Citas:
---------- APA ----------
Varela, O. & Zunszain, P.A.
(1993)
. First Synthesis of Aldopentono-1,4-thiolactones. Journal of Organic Chemistry, 58(27), 7860-7864.
http://dx.doi.org/10.1021/jo00079a034---------- CHICAGO ----------
Varela, O., Zunszain, P.A.
"First Synthesis of Aldopentono-1,4-thiolactones"
. Journal of Organic Chemistry 58, no. 27
(1993) : 7860-7864.
http://dx.doi.org/10.1021/jo00079a034---------- MLA ----------
Varela, O., Zunszain, P.A.
"First Synthesis of Aldopentono-1,4-thiolactones"
. Journal of Organic Chemistry, vol. 58, no. 27, 1993, pp. 7860-7864.
http://dx.doi.org/10.1021/jo00079a034---------- VANCOUVER ----------
Varela, O., Zunszain, P.A. First Synthesis of Aldopentono-1,4-thiolactones. J. Org. Chem. 1993;58(27):7860-7864.
http://dx.doi.org/10.1021/jo00079a034