Navegar

Colección

Datos Estadísticas

Artículo

La versión final de este artículo es de uso interno. El editor solo permite incluir en el repositorio el artículo en su versión post-print. Por favor, si usted la posee enviela a
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

2-Acetoxy-3,4-di-O-acetyl-D-arabinal (6), similar to its D-xylo analogue 4, reacted with benzyl alcohol by the tin(IV) chloride-promoted glycosylation to produce optically active (S)-2-benzyloxy-2H-pyran-3(6H)-one (8a). The L-arabinal derivative (5) gave 9a, the dihydropyranone enantiomer of 8a. These results indicated that the configuration of the C-4 stereocenter in the starting glycal defines the configuration of the new chiral center in the resulting dihydropyranone. The influence of other catalysts (BF3 or iodine) employed for the glycosylation on the optical purity of the dihydropyranone was studied. Enantiomerically pure dihydropyranones 8b and 9c were obtained using chiral alcohols ((R)- and (S)-2-octanol, respectively) as glycosylating agents. Compounds 8a,b and 9a,c proved to be reactive dienophiles in thermal and Lewis acid-promoted Diels - Alder reactions. The addition of 2,3-dimethylbutadiene, cyclopentadiene, and 1,3-cyclohexadiene to the β-pyranones 8a,b led to the corresponding adducts 10a,b, 12a,b, and 16a,b as major products. Enantiomeric cycloadducts were synthesized from the α-pyranones 9a,c. The main products were formed by highly facial-diastereoselective addition of dienes to the pyranone ring, guided by the sterical hindrance of the alkoxy substituent of the C-2 stereocenter. As cycloadditions with cycloalkadienes were also highly endo diastereoselective, these reactions gave access to pure tetrahydrobenzopyranones that carry a multitude of stereogenic centers installed in a predictable way.

Registro:

Documento: Artículo
Título:Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes
Autor:Iriarte Capaccio, C.A.; Varela, O.
Filiación:CIHIDECAR-CONICET, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2-Ciudad Universitaria, 1428, Buenos Aires, Argentina
Palabras clave:Diastereoselectivity; Enantiomers; Addition reactions; Alcohols; Catalysts; Olefins; Stereochemistry; Synthesis (chemical); Ketones; 1,3 butadiene derivative; 1,3 cyclohexadiene; 2 acetoxy 3,4 di o acetyl dextro arabinal; 2 benzyloxy 2h pyran 3(6h) one; 2,3 dimethylbutadiene; alkadiene; arabinose derivative; cyclopentadiene derivative; dihydropyranone derivative; pyran derivative; tetrahydrobenzopyranone derivative; unclassified drug; article; catalysis; chirality; cycloaddition; enantiomer; optics; prediction; protein glycosylation; reaction analysis; stereochemistry; stereospecificity; synthesis; thermal analysis; Carbohydrates; Hydroxylation; Molecular Structure; Pyrones; Stereoisomerism; Temperature
Año:2002
Volumen:67
Número:22
Página de inicio:7839
Página de fin:7846
DOI: http://dx.doi.org/10.1021/jo020309w
Título revista:Journal of Organic Chemistry
Título revista abreviado:J. Org. Chem.
ISSN:00223263
CODEN:JOCEA
CAS:1,3 cyclohexadiene, 592-57-4; 2,3 dimethylbutadiene, 513-81-5; Carbohydrates; Pyrones
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v67_n22_p7839_IriarteCapaccio

Referencias:

  • Lichtenthaler, F.W., Nishiyama, S., Weimer, T., (1989) Liebigs Ann. Chem., 1163
  • Lichtenthaler, F.W., (1992) Modern Synthetic Methods, 6, p. 273. , Scheffold R. Ed.; VCH Publishers, Weinheim/New York
  • Lichtenthaler, F.W., (1986) Natural Products Chemistry, p. 227. , Attaur-Rahman, Ed.; Springer, New York
  • Fraser-Reid, B., (1996) Acc. Chem. Res., 29, p. 57
  • De Fina, G.M., Varela, O., Lederkremer, R.M., (1988) Synthesis, 891
  • Iriarte Capaccio, C.A., Varela, O., (2000) Tetrahedron: Asymmetry, 11, p. 4945
  • Zunszain, P.A., Varela, O., (1998) Tetrahedron: Asymmetry, 9, p. 1269
  • Varela, O., De Fina, G.M., Lederkremer, R.M., (1993) Carbohydr. Res., 246, p. 371
  • Iriarte Capaccio, C.A., Varela, O., (2001) J. Org. Chem., 66, p. 8859
  • Fraser-Reid, B., Underwood, R., Osterhout, M., Grossman, J.A., Liotta, D., (1986) J. Org. Chem., 51, p. 2152
  • Primeau, J.L., Anderson, R.C., Fraser-Reid, B., (1980) J. Chem. Soc., Chem. Commun., p. 6
  • Jurczak, J., Tkacz, M., (1979) Synthesis, p. 42
  • Dauben, W.G., Kowalczyk, B.A., Lichtenthaler, F.W., (1990) J. Org. Chem., 55, p. 2391
  • Bhaté, P., Horton, D., (1983) Carbohydr. Res., 122, p. 189
  • Shafizadeh, F., Essig, M.G., Ward, D.D., (1983) Carbohydr. Res., 114, p. 71
  • Ward, D.D., Shafizadeh, F., (1981) Carbohydr. Res., 95, p. 155
  • Horton, D., Roski, J.P., Norris, P., (1996) J. Org. Chem., 61, p. 3783
  • Fringuelli, F., Pizzo, F., Taticchi, A., Wenkert, E., (1983) J. Org. Chem., 48, p. 2802
  • Fringuelli, F., Pizzo, F., Taticchi, A., Halls, T.D.J., Wenkert, E., (1982) J. Org. Chem., 47, p. 5056
  • Rico, M., Santoro, J., (1976) Org. Magn. Reson., 8, p. 49
  • Chalmers, A.A., Hall, R.H., (1974) J. Chem. Soc., Perkin Trans. 2, p. 728
  • Ferrier, R.J., Prasad, N., Sankey, G.H., (1968) J. Chem. Soc., 974
  • Vaino, A.R., Szarek, W.A., (2001) Adv. Carbohydr. Chem. Biochem., 56, p. 9
  • Varela, O., De Fina, G.M., Lederkremer, R.M., (1987) Carbohydr. Res., 167, p. 187
  • Alder, K., Stein, G., (1937) Angew. Chem., 50, p. 510
  • Gleiter, R., Bohm, M.C., (1983) Pure Appl. Chem., 55, p. 237
  • Ginsburg, D., (1983) Tetrahedron, 39, p. 2095
  • Fringuelli, F., Guo, M., Minuti, L., Pizzo, F., Taticchi, A., Wenkert, E., (1989) J. Org. Chem., 54, p. 710
  • Angell, E.C., Fringuelli, F., Guo, M., Minuti, L., Taticchi, A., Wenkert, E., (1988) J. Org. Chem., 53, p. 4325
  • Bodenhausen, G., Ernst, R.R., (1982) J. Am. Chem. Soc., 104, p. 1304
  • Derome, A.E., (1997) Modern NMR Techniques for Chemistry Research, Tetrahedron Organic Chemistry Series, 6, p. 239. , Baldwin J. E., Magnus P. D., Eds.; Pergamon: Oxford
  • Bock, K., Pedersen, C., (1970) Acta Chem. Scand., 24, p. 2465

Citas:

---------- APA ----------
Iriarte Capaccio, C.A. & Varela, O. (2002) . Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes. Journal of Organic Chemistry, 67(22), 7839-7846.
http://dx.doi.org/10.1021/jo020309w
---------- CHICAGO ----------
Iriarte Capaccio, C.A., Varela, O. "Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes" . Journal of Organic Chemistry 67, no. 22 (2002) : 7839-7846.
http://dx.doi.org/10.1021/jo020309w
---------- MLA ----------
Iriarte Capaccio, C.A., Varela, O. "Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes" . Journal of Organic Chemistry, vol. 67, no. 22, 2002, pp. 7839-7846.
http://dx.doi.org/10.1021/jo020309w
---------- VANCOUVER ----------
Iriarte Capaccio, C.A., Varela, O. Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes. J. Org. Chem. 2002;67(22):7839-7846.
http://dx.doi.org/10.1021/jo020309w