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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todo:paper_00086215_v340_n13_p2104_Capaccio2023-10-03T14:07:07Z Sugar-derived 2-S-substituted-2H-pyran-3(6H)-ones: Synthesis and reactivity Capaccio, C.A.I. Varela, O. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00086215_v340_n13_p2104_Capaccio |
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Universidad de Buenos Aires |
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I-28 |
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R-134 |
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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 Capaccio, C.A.I. Varela, O. 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. |
| format |
JOUR |
| author |
Capaccio, C.A.I. Varela, O. |
| author_facet |
Capaccio, C.A.I. Varela, O. |
| author_sort |
Capaccio, C.A.I. |
| 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 |
| url |
http://hdl.handle.net/20.500.12110/paper_00086215_v340_n13_p2104_Capaccio |
| work_keys_str_mv |
AT capacciocai sugarderived2ssubstituted2hpyran36honessynthesisandreactivity AT varelao sugarderived2ssubstituted2hpyran36honessynthesisandreactivity |
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1807318797714980864 |