Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes
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. The...
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todo:paper_00223263_v67_n22_p7839_IriarteCapaccio2023-10-03T14:31:25Z Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes Iriarte Capaccio, C.A. Varela, O. 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 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. Fil:Iriarte Capaccio, C.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Varela, O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00223263_v67_n22_p7839_IriarteCapaccio |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
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 |
| spellingShingle |
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 Iriarte Capaccio, C.A. Varela, O. Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes |
| topic_facet |
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 |
| description |
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. |
| format |
JOUR |
| author |
Iriarte Capaccio, C.A. Varela, O. |
| author_facet |
Iriarte Capaccio, C.A. Varela, O. |
| author_sort |
Iriarte Capaccio, C.A. |
| title |
Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes |
| title_short |
Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes |
| title_full |
Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes |
| title_fullStr |
Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes |
| title_full_unstemmed |
Stereocontrolled Diels - Alder cycloadditions of sugar-derived dihydropyranones with dienes |
| title_sort |
stereocontrolled diels - alder cycloadditions of sugar-derived dihydropyranones with dienes |
| url |
http://hdl.handle.net/20.500.12110/paper_00223263_v67_n22_p7839_IriarteCapaccio |
| work_keys_str_mv |
AT iriartecapaccioca stereocontrolleddielsaldercycloadditionsofsugarderiveddihydropyranoneswithdienes AT varelao stereocontrolleddielsaldercycloadditionsofsugarderiveddihydropyranoneswithdienes |
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