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
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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
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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
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Volumen: | 67
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Número: | 22
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Página de inicio: | 7839
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Página de fin: | 7846
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DOI: |
http://dx.doi.org/10.1021/jo020309w |
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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CODEN: | JOCEA
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CAS: | 1,3 cyclohexadiene, 592-57-4; 2,3 dimethylbutadiene, 513-81-5; Carbohydrates; Pyrones
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v67_n22_p7839_IriarteCapaccio |
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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