Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity
A practical procedure for the preparation of chiral 2-S-substituted-2H- pyran-3(6H)-ones is described. According to the reaction conditions, 1,5-anhydro-2,3,4-tri-O-acetyl-d-threo-pent-1-enitol (1) reacted with thiophenol under Lewis acid catalysis to afford the polysubstitution product 1,5-anhydro-...
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2005
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v340_n13_p2104_Capaccio http://hdl.handle.net/20.500.12110/paper_00086215_v340_n13_p2104_Capaccio |
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paper:paper_00086215_v340_n13_p2104_Capaccio2023-06-08T14:32:49Z Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity Varela, Oscar José Dihydropyranone Glycosylations Iodine Lewis acids Thiols Catalysis Iodine Reduction Substitution reactions Synthesis (chemical) Dihydropyranone Glycosylations Lewis acids Polysubstitution Thiols Sugar (sucrose) 1,5 anhydro 2,3,4 tri o acetyl dextro threo pent 1 enitol 1,5 anhydro 2,3,4 tri s phenyl 2,3,4 trithio dextro,levo threo pent 1 enitol 2 benzylthio 2h pyran 3(6h) one 2 phenylthio 2h pyran pyran 3(6h) one acetonitrile alcohol derivative carbonyl derivative iodine Lewis acid phenyl 2,4 di o acetyl 3 deoxy 1 thio alpha dextro glyceropent 2 enopyranoside phenyl 2,4 di o acetyl 3 deoxy 1 thio beta dextro glyceropent 2 enopyranoside pyran derivative pyranoside sugar thiol derivative thiophenol unclassified drug article catalysis chirality cycloaddition enantiomer priority journal stereochemistry synthesis Pentoses Phenols Pyrans Stereoisomerism Sulfhydryl Compounds A practical procedure for the preparation of chiral 2-S-substituted-2H- pyran-3(6H)-ones is described. According to the reaction conditions, 1,5-anhydro-2,3,4-tri-O-acetyl-d-threo-pent-1-enitol (1) reacted with thiophenol under Lewis acid catalysis to afford the polysubstitution product 1,5-anhydro-2,3,4-tri-S-phenyl-2,3,4-trithio-d,l-threo-pent-1-enitol (2) or phenyl 2,4-di-O-acetyl-3-deoxy-1-thio-α- and β-d-glycero-pent-2- enopyranoside (3 and 4, respectively). The iodine-promoted addition of thiophenol or α-toluenethiol to 1 gave (2S)-2-phenylthio-2H-pyran-3(6H)- one (5) or its 2-benzylthio analogue 6, but these products showed low enantiomeric excesses (ee ∼40-60%). However, dihydropyranone 5 with high optical purity (ee >94%) was successfully obtained by treatment of 4 with iodine in acetonitrile. On the other hand, it was established that the benzylthio group of 5 exerts high stereocontrol in reduction and cycloaddition reactions performed on the α,β-unsaturated carbonyl system. © 2005 Elsevier Ltd. All rights reserved. Fil:Varela, O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2005 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v340_n13_p2104_Capaccio http://hdl.handle.net/20.500.12110/paper_00086215_v340_n13_p2104_Capaccio |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Dihydropyranone Glycosylations Iodine Lewis acids Thiols Catalysis Iodine Reduction Substitution reactions Synthesis (chemical) Dihydropyranone Glycosylations Lewis acids Polysubstitution Thiols Sugar (sucrose) 1,5 anhydro 2,3,4 tri o acetyl dextro threo pent 1 enitol 1,5 anhydro 2,3,4 tri s phenyl 2,3,4 trithio dextro,levo threo pent 1 enitol 2 benzylthio 2h pyran 3(6h) one 2 phenylthio 2h pyran pyran 3(6h) one acetonitrile alcohol derivative carbonyl derivative iodine Lewis acid phenyl 2,4 di o acetyl 3 deoxy 1 thio alpha dextro glyceropent 2 enopyranoside phenyl 2,4 di o acetyl 3 deoxy 1 thio beta dextro glyceropent 2 enopyranoside pyran derivative pyranoside sugar thiol derivative thiophenol unclassified drug article catalysis chirality cycloaddition enantiomer priority journal stereochemistry synthesis Pentoses Phenols Pyrans Stereoisomerism Sulfhydryl Compounds |
| spellingShingle |
Dihydropyranone Glycosylations Iodine Lewis acids Thiols Catalysis Iodine Reduction Substitution reactions Synthesis (chemical) Dihydropyranone Glycosylations Lewis acids Polysubstitution Thiols Sugar (sucrose) 1,5 anhydro 2,3,4 tri o acetyl dextro threo pent 1 enitol 1,5 anhydro 2,3,4 tri s phenyl 2,3,4 trithio dextro,levo threo pent 1 enitol 2 benzylthio 2h pyran 3(6h) one 2 phenylthio 2h pyran pyran 3(6h) one acetonitrile alcohol derivative carbonyl derivative iodine Lewis acid phenyl 2,4 di o acetyl 3 deoxy 1 thio alpha dextro glyceropent 2 enopyranoside phenyl 2,4 di o acetyl 3 deoxy 1 thio beta dextro glyceropent 2 enopyranoside pyran derivative pyranoside sugar thiol derivative thiophenol unclassified drug article catalysis chirality cycloaddition enantiomer priority journal stereochemistry synthesis Pentoses Phenols Pyrans Stereoisomerism Sulfhydryl Compounds Varela, Oscar José Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity |
| topic_facet |
Dihydropyranone Glycosylations Iodine Lewis acids Thiols Catalysis Iodine Reduction Substitution reactions Synthesis (chemical) Dihydropyranone Glycosylations Lewis acids Polysubstitution Thiols Sugar (sucrose) 1,5 anhydro 2,3,4 tri o acetyl dextro threo pent 1 enitol 1,5 anhydro 2,3,4 tri s phenyl 2,3,4 trithio dextro,levo threo pent 1 enitol 2 benzylthio 2h pyran 3(6h) one 2 phenylthio 2h pyran pyran 3(6h) one acetonitrile alcohol derivative carbonyl derivative iodine Lewis acid phenyl 2,4 di o acetyl 3 deoxy 1 thio alpha dextro glyceropent 2 enopyranoside phenyl 2,4 di o acetyl 3 deoxy 1 thio beta dextro glyceropent 2 enopyranoside pyran derivative pyranoside sugar thiol derivative thiophenol unclassified drug article catalysis chirality cycloaddition enantiomer priority journal stereochemistry synthesis Pentoses Phenols Pyrans Stereoisomerism Sulfhydryl Compounds |
| description |
A practical procedure for the preparation of chiral 2-S-substituted-2H- pyran-3(6H)-ones is described. According to the reaction conditions, 1,5-anhydro-2,3,4-tri-O-acetyl-d-threo-pent-1-enitol (1) reacted with thiophenol under Lewis acid catalysis to afford the polysubstitution product 1,5-anhydro-2,3,4-tri-S-phenyl-2,3,4-trithio-d,l-threo-pent-1-enitol (2) or phenyl 2,4-di-O-acetyl-3-deoxy-1-thio-α- and β-d-glycero-pent-2- enopyranoside (3 and 4, respectively). The iodine-promoted addition of thiophenol or α-toluenethiol to 1 gave (2S)-2-phenylthio-2H-pyran-3(6H)- one (5) or its 2-benzylthio analogue 6, but these products showed low enantiomeric excesses (ee ∼40-60%). However, dihydropyranone 5 with high optical purity (ee >94%) was successfully obtained by treatment of 4 with iodine in acetonitrile. On the other hand, it was established that the benzylthio group of 5 exerts high stereocontrol in reduction and cycloaddition reactions performed on the α,β-unsaturated carbonyl system. © 2005 Elsevier Ltd. All rights reserved. |
| author |
Varela, Oscar José |
| author_facet |
Varela, Oscar José |
| author_sort |
Varela, Oscar José |
| title |
Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity |
| title_short |
Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity |
| title_full |
Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity |
| title_fullStr |
Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity |
| title_full_unstemmed |
Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity |
| title_sort |
sugar-derived 2-s-substituted-2h-pyran-3(6h)-ones: synthesis and reactivity |
| publishDate |
2005 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v340_n13_p2104_Capaccio http://hdl.handle.net/20.500.12110/paper_00086215_v340_n13_p2104_Capaccio |
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AT varelaoscarjose sugarderived2ssubstituted2hpyran36honessynthesisandreactivity |
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1768543928003330048 |