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Abstract:

Michael addition of common thiols to the enone system of (2S)-2-benzyloxy-2H-pyran-3(6H)-one (1) afforded the corresponding 3-deoxy-4-thiopentopyranosid-2-ulose derivatives (2-4). The reaction was highly diastereoselective, and the addition was governed by the quasiaxially disposed 2-benzyloxy substituent of the starting pyranone. As expected from the enantiomeric excess of 1 (ee >86%) the corresponding thiouloses 2-4 exhibited the same optical purity. However, the enantiomerically pure thioulose 5 was obtained by reaction of 1 with the chiral thiol, N-(tert-butoxycarbonyl)-L-cysteine methyl ester. The thio derivative 7 was also synthesized by reaction of 6 (enantiomer of 1) with the same chiral thiol. Alternatively, 4-thiopent-2-uloses 9-12 were prepared in high optical purity by 1,4-addition of thiols to (2S)-[(S)-2′-octyloxy]dihydropyranone 8. Similarly, reaction of 13 (enantiomer of 8) with benzenemethanethiol afforded 14 (enantiomer of 10). This way, the stereocontrol exerted by the anomeric center on the starting dihydropyranone led to 4-thiopentuloses of the D and L series. Sodium borohydride reduction of the carbonyl function of uloses 10 and 12 gave the corresponding 3-deoxy-4-thiopentopyranosid-2-uloses (16-19). The diastereomers having the β-D-threo configuration (16, 18) slightly predominated over the β-D-erythro (17, 19) analogues. However, the reduction of the enantiomeric pyranones 10 and 14 with K-Selectride® was highly diastereofacial selective in favor of the β-D- and β-L-threo isomers 16 and 20, respectively. © 2002 Elsevier Science Ltd. All rights reserved.

Registro:

Documento: Artículo
Título:Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides
Autor:Uhrig, M.L.; Varela, O.
Filiación:CIHIDECAR-CONICET, Departamento De Química Orgánica, Niversidad De Buenos Aires, 1428, Buenos Aires, Argentina
Palabras clave:3-Deoxy-4-thiopentopyranosid-2-uloses; 3-Deoxy-4-thiopentopyranosides; Michael addition; Thio sugars; Addition reactions; Derivatives; Esters; Isomers; Stereochemistry; Synthesis (chemical); Stereocontrols; Carbohydrates; 2 octyl 2 o acetyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro threo beta dextro erythro pentapyranoside; 2 octyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro glyceropentopyranosid 2 ulose; 2 octyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose; 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose; 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro threo pentopyranoside; 2 octyl 4 s benzyl 3 deoxy 4 thio beta levo glyceropentopyranosid 2 ulose; 3 deoxy 4 thiopentopyranosid 2 ulose; benzyl 3 deoxy 4 s (2 propyl) 4 thio beta dextro glyceropentopyranosid 2 ulose; benzyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose; benzyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose; cysteine derivative; glycoside; n (tert butoxycarbonyl)cysteine; pyranosid 2 ulose; pyranoside; thiol derivative; unclassified drug; article; chemical reaction; enantiomer; isomer; optical rotation; priority journal; proton nuclear magnetic resonance; reduction; stereochemistry; synthesis; thin layer chromatography; Carbohydrate Conformation; Glycosides; Magnetic Resonance Spectroscopy; Pentoses; Stereoisomerism; Sulfhydryl Compounds; Thioglycosides
Año:2002
Volumen:337
Número:21-23
Página de inicio:2069
Página de fin:2076
DOI: http://dx.doi.org/10.1016/S0008-6215(02)00292-6
Título revista:Carbohydrate Research
Título revista abreviado:Carbohydr. Res.
ISSN:00086215
CODEN:CRBRA
CAS:Glycosides; Pentoses; Sulfhydryl Compounds; Thioglycosides
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v337_n21-23_p2069_Uhrig

Referencias:

  • Witczak, Z.J., (1999) Curr. Med. Chem., 6, pp. 165-178
  • Becker, B., (2000) J. Carbohydr. Chem., 19, pp. 253-284
  • Shafizadeh, F., Fourneaux, H., Stevenson, T.T., (1979) Carbohydr. Res., 71, pp. 169-191
  • Essig, M.G., (1986) Carbohydr. Res., 156, pp. 225-231
  • Gomez, M., Quincoces, J., Kuhla, B., Peseke, K., Reinke, H., (1999) J. Carbohydr. Chem., 18, pp. 57-68
  • Michael, K., Kessler, H., (1996) Tetrahedron Lett., 37, pp. 3453-3456
  • Witczak, Z.J., Sun, J., Mielguj, R., (1995) Bioorg. Med. Chem. Lett., 5, pp. 2169-2174
  • Witczak, Z.J., Chhabra, R., Chen, H., Xie, X.-Q., (1997) Carbohydr. Res., 301, pp. 167-175. , and references therein
  • Kroutil, J., Cerný, M., Trnka, T., Budešínsky, M., (2001) Carbohydr. Res., 334, pp. 153-158
  • Witczak, Z.J., Chen, H., Kaplon, P., (2000) Tetrahedron: Asymmetry, 11, pp. 519-532
  • Gomez, M., Quincoces, J., Peseke, K., Michalik, M., Reinke, H., (1999) J. Carbohydr. Chem., 18, pp. 851-865
  • De Fina, G., Varela, O., Lederkremer, R.M., (1988) Synthesis, pp. 891-893
  • Iriarte-Capaccio, C., Varela, O., (2001) J. Org. Chem., 66, pp. 8859-8866
  • Varela, O., De Fina, G., Lederkremer, R.M., (1993) Carbohydr. Res., 246, pp. 371-376
  • Varela, O., De Fina, G., Lederkremer, R.M., (1990) J. Chem. Res. (S), pp. 262-263
  • Zunszain, P.A., Varela, O., (1998) Tetrahedron: Asymmetry, 9, pp. 1269-1276
  • Iriarte-Capaccio, C., Varela, O., (2000) Tetrahedron: Asymmetry, 11, pp. 4945-4954
  • Uhrig, M.L., Varela, O., (2002) Aust. J. Chem., 55, pp. 155-160
  • Dauben, W.G., Kowalczyk, B.A., Lichtenthaler, F.W., (1990) J. Org. Chem., 55, pp. 2391-2398
  • Horton, D., Durette, P.L., Wander, J., (1973) Ann. NY Acad. Sci., 222, pp. 884-914
  • Durette, P.L., Horton, D., (1971) Adv. Carbohydr. Chem. Biochem., 26, pp. 49-125
  • Lichtenthaler, F.W., Nishiyama, S., Köhler, P., Linder, H.J., (1985) Carbohydr. Res., 136, pp. 13-26
  • Bock, K., Pedersen, C., (1983) Adv. Carbohydr. Chem. Biochem., 41, pp. 27-66
  • Haque, M.E., Kikuchi, T., Kanemitsu, K., Tsuda, Y., (1987) Chem. Pharm. Bull., 35, pp. 1016-1029

Citas:

---------- APA ----------
Uhrig, M.L. & Varela, O. (2002) . Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides. Carbohydrate Research, 337(21-23), 2069-2076.
http://dx.doi.org/10.1016/S0008-6215(02)00292-6
---------- CHICAGO ----------
Uhrig, M.L., Varela, O. "Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides" . Carbohydrate Research 337, no. 21-23 (2002) : 2069-2076.
http://dx.doi.org/10.1016/S0008-6215(02)00292-6
---------- MLA ----------
Uhrig, M.L., Varela, O. "Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides" . Carbohydrate Research, vol. 337, no. 21-23, 2002, pp. 2069-2076.
http://dx.doi.org/10.1016/S0008-6215(02)00292-6
---------- VANCOUVER ----------
Uhrig, M.L., Varela, O. Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides. Carbohydr. Res. 2002;337(21-23):2069-2076.
http://dx.doi.org/10.1016/S0008-6215(02)00292-6