Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides
Michael addition of common thiols to the enone system of (2S)-2-benzyloxy-2H-pyran-3(6H)-one (1) afforded the corresponding 3-deoxy-4-thiopentopyranosid-2-ulose derivatives (2-4). The reaction was highly diastereoselective, and the addition was governed by the quasiaxially disposed 2-benzyloxy subst...
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2002
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v337_n21-23_p2069_Uhrig http://hdl.handle.net/20.500.12110/paper_00086215_v337_n21-23_p2069_Uhrig |
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paper:paper_00086215_v337_n21-23_p2069_Uhrig2023-06-08T14:32:42Z Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides 3-Deoxy-4-thiopentopyranosid-2-uloses 3-Deoxy-4-thiopentopyranosides Michael addition Thio sugars Addition reactions Derivatives Esters Isomers Stereochemistry Synthesis (chemical) Stereocontrols Carbohydrates 2 octyl 2 o acetyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro threo beta dextro erythro pentapyranoside 2 octyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro threo pentopyranoside 2 octyl 4 s benzyl 3 deoxy 4 thio beta levo glyceropentopyranosid 2 ulose 3 deoxy 4 thiopentopyranosid 2 ulose benzyl 3 deoxy 4 s (2 propyl) 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose cysteine derivative glycoside n (tert butoxycarbonyl)cysteine pyranosid 2 ulose pyranoside thiol derivative unclassified drug article chemical reaction enantiomer isomer optical rotation priority journal proton nuclear magnetic resonance reduction stereochemistry synthesis thin layer chromatography Carbohydrate Conformation Glycosides Magnetic Resonance Spectroscopy Pentoses Stereoisomerism Sulfhydryl Compounds Thioglycosides Michael addition of common thiols to the enone system of (2S)-2-benzyloxy-2H-pyran-3(6H)-one (1) afforded the corresponding 3-deoxy-4-thiopentopyranosid-2-ulose derivatives (2-4). The reaction was highly diastereoselective, and the addition was governed by the quasiaxially disposed 2-benzyloxy substituent of the starting pyranone. As expected from the enantiomeric excess of 1 (ee >86%) the corresponding thiouloses 2-4 exhibited the same optical purity. However, the enantiomerically pure thioulose 5 was obtained by reaction of 1 with the chiral thiol, N-(tert-butoxycarbonyl)-L-cysteine methyl ester. The thio derivative 7 was also synthesized by reaction of 6 (enantiomer of 1) with the same chiral thiol. Alternatively, 4-thiopent-2-uloses 9-12 were prepared in high optical purity by 1,4-addition of thiols to (2S)-[(S)-2′-octyloxy]dihydropyranone 8. Similarly, reaction of 13 (enantiomer of 8) with benzenemethanethiol afforded 14 (enantiomer of 10). This way, the stereocontrol exerted by the anomeric center on the starting dihydropyranone led to 4-thiopentuloses of the D and L series. Sodium borohydride reduction of the carbonyl function of uloses 10 and 12 gave the corresponding 3-deoxy-4-thiopentopyranosid-2-uloses (16-19). The diastereomers having the β-D-threo configuration (16, 18) slightly predominated over the β-D-erythro (17, 19) analogues. However, the reduction of the enantiomeric pyranones 10 and 14 with K-Selectride® was highly diastereofacial selective in favor of the β-D- and β-L-threo isomers 16 and 20, respectively. © 2002 Elsevier Science Ltd. All rights reserved. 2002 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v337_n21-23_p2069_Uhrig http://hdl.handle.net/20.500.12110/paper_00086215_v337_n21-23_p2069_Uhrig |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
3-Deoxy-4-thiopentopyranosid-2-uloses 3-Deoxy-4-thiopentopyranosides Michael addition Thio sugars Addition reactions Derivatives Esters Isomers Stereochemistry Synthesis (chemical) Stereocontrols Carbohydrates 2 octyl 2 o acetyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro threo beta dextro erythro pentapyranoside 2 octyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro threo pentopyranoside 2 octyl 4 s benzyl 3 deoxy 4 thio beta levo glyceropentopyranosid 2 ulose 3 deoxy 4 thiopentopyranosid 2 ulose benzyl 3 deoxy 4 s (2 propyl) 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose cysteine derivative glycoside n (tert butoxycarbonyl)cysteine pyranosid 2 ulose pyranoside thiol derivative unclassified drug article chemical reaction enantiomer isomer optical rotation priority journal proton nuclear magnetic resonance reduction stereochemistry synthesis thin layer chromatography Carbohydrate Conformation Glycosides Magnetic Resonance Spectroscopy Pentoses Stereoisomerism Sulfhydryl Compounds Thioglycosides |
| spellingShingle |
3-Deoxy-4-thiopentopyranosid-2-uloses 3-Deoxy-4-thiopentopyranosides Michael addition Thio sugars Addition reactions Derivatives Esters Isomers Stereochemistry Synthesis (chemical) Stereocontrols Carbohydrates 2 octyl 2 o acetyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro threo beta dextro erythro pentapyranoside 2 octyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro threo pentopyranoside 2 octyl 4 s benzyl 3 deoxy 4 thio beta levo glyceropentopyranosid 2 ulose 3 deoxy 4 thiopentopyranosid 2 ulose benzyl 3 deoxy 4 s (2 propyl) 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose cysteine derivative glycoside n (tert butoxycarbonyl)cysteine pyranosid 2 ulose pyranoside thiol derivative unclassified drug article chemical reaction enantiomer isomer optical rotation priority journal proton nuclear magnetic resonance reduction stereochemistry synthesis thin layer chromatography Carbohydrate Conformation Glycosides Magnetic Resonance Spectroscopy Pentoses Stereoisomerism Sulfhydryl Compounds Thioglycosides Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides |
| topic_facet |
3-Deoxy-4-thiopentopyranosid-2-uloses 3-Deoxy-4-thiopentopyranosides Michael addition Thio sugars Addition reactions Derivatives Esters Isomers Stereochemistry Synthesis (chemical) Stereocontrols Carbohydrates 2 octyl 2 o acetyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro threo beta dextro erythro pentapyranoside 2 octyl 3 deoxy 4 s [methyl n (tert butoxycarbonyl)cysteinat 3 yl] 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose 2 octyl 4 s benzyl 3 deoxy 4 thio beta dextro threo pentopyranoside 2 octyl 4 s benzyl 3 deoxy 4 thio beta levo glyceropentopyranosid 2 ulose 3 deoxy 4 thiopentopyranosid 2 ulose benzyl 3 deoxy 4 s (2 propyl) 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 3 deoxy 4 s ethyl 4 thio beta dextro glyceropentopyranosid 2 ulose benzyl 4 s benzyl 3 deoxy 4 thio beta dextro glyceropentopyranosid 2 ulose cysteine derivative glycoside n (tert butoxycarbonyl)cysteine pyranosid 2 ulose pyranoside thiol derivative unclassified drug article chemical reaction enantiomer isomer optical rotation priority journal proton nuclear magnetic resonance reduction stereochemistry synthesis thin layer chromatography Carbohydrate Conformation Glycosides Magnetic Resonance Spectroscopy Pentoses Stereoisomerism Sulfhydryl Compounds Thioglycosides |
| description |
Michael addition of common thiols to the enone system of (2S)-2-benzyloxy-2H-pyran-3(6H)-one (1) afforded the corresponding 3-deoxy-4-thiopentopyranosid-2-ulose derivatives (2-4). The reaction was highly diastereoselective, and the addition was governed by the quasiaxially disposed 2-benzyloxy substituent of the starting pyranone. As expected from the enantiomeric excess of 1 (ee >86%) the corresponding thiouloses 2-4 exhibited the same optical purity. However, the enantiomerically pure thioulose 5 was obtained by reaction of 1 with the chiral thiol, N-(tert-butoxycarbonyl)-L-cysteine methyl ester. The thio derivative 7 was also synthesized by reaction of 6 (enantiomer of 1) with the same chiral thiol. Alternatively, 4-thiopent-2-uloses 9-12 were prepared in high optical purity by 1,4-addition of thiols to (2S)-[(S)-2′-octyloxy]dihydropyranone 8. Similarly, reaction of 13 (enantiomer of 8) with benzenemethanethiol afforded 14 (enantiomer of 10). This way, the stereocontrol exerted by the anomeric center on the starting dihydropyranone led to 4-thiopentuloses of the D and L series. Sodium borohydride reduction of the carbonyl function of uloses 10 and 12 gave the corresponding 3-deoxy-4-thiopentopyranosid-2-uloses (16-19). The diastereomers having the β-D-threo configuration (16, 18) slightly predominated over the β-D-erythro (17, 19) analogues. However, the reduction of the enantiomeric pyranones 10 and 14 with K-Selectride® was highly diastereofacial selective in favor of the β-D- and β-L-threo isomers 16 and 20, respectively. © 2002 Elsevier Science Ltd. All rights reserved. |
| title |
Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides |
| title_short |
Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides |
| title_full |
Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides |
| title_fullStr |
Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides |
| title_full_unstemmed |
Synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-Deoxy-4-thiopentopyranosides |
| title_sort |
synthesis of glycosides of 3-deoxy-4-thiopentopyranosid-2-uloses and their reduction products: 3-deoxy-4-thiopentopyranosides |
| publishDate |
2002 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v337_n21-23_p2069_Uhrig http://hdl.handle.net/20.500.12110/paper_00086215_v337_n21-23_p2069_Uhrig |
| _version_ |
1768544758139977728 |