Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration
Methyl 2,3-di-O-benzoyl-6-deoxy-4-O-(p-tolylsulfonyl) and 4-O-[(p-nitrophenyl)sulfonyl]-α-d-mannopyranosides (9 and 10) were prepared by three different routes from methyl α-d-mannopyranoside (1). The analogous 4-sulfonyloxy derivatives having HO-2 and HO-3 free (14 and 15) were also synthesized fro...
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todo:paper_00086215_v211_n2_p295_Cicero2023-10-03T14:06:34Z Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration Cicero, D. Varela, O. De Lederkremer, R.M. carbohydrate derivative sugar article chemical structure nuclear magnetic resonance synthesis Methyl 2,3-di-O-benzoyl-6-deoxy-4-O-(p-tolylsulfonyl) and 4-O-[(p-nitrophenyl)sulfonyl]-α-d-mannopyranosides (9 and 10) were prepared by three different routes from methyl α-d-mannopyranoside (1). The analogous 4-sulfonyloxy derivatives having HO-2 and HO-3 free (14 and 15) were also synthesized from 1. Nucleophilic substitution of the sulfonyloxy group of 9, 10, 14, and 15 by potassium thiocyanate in N,N-dimethylformamide was attempted. Compounds 9 and 10 gave a mixture of solvolysis products: methyl 2,3-di-O-benzoyl-6-deoxy-α-d-talopyranoside (17), methyl 3,4-di-O-benzoyl-6-deoxy-α-d-talopyranoside (18), and methyl 2,4-di-O-benzoyl-6-deoxy-α-d-talopyranoside (19), which are evidently formed by intramolecular displacement of the 4-sulfonate by backside attack of the C-2 benzoyloxy substituent, followed by benzoyl migration. The structure of compounds 17-19 was established by spectroscopic analysis, and then chemically confirmed. Although compound 14 decomposed during the substitution reaction, the 4-p-nitrophenylsulfonyl derivative 15 gave a 2:1 mixture of the 4-thiocyano derivatives with inversion [methyl 4,6-dideoxy-4-thiocyano-α-d-talopyranoside (22)] and retention [methyl 4,6-dideoxy-4-thiocyano-α-d-mannopyranoside (23)] of the C-4 configuration. © 1991. Fil:Cicero, D. 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. Fil:De Lederkremer, R.M. 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_v211_n2_p295_Cicero |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
carbohydrate derivative sugar article chemical structure nuclear magnetic resonance synthesis |
| spellingShingle |
carbohydrate derivative sugar article chemical structure nuclear magnetic resonance synthesis Cicero, D. Varela, O. De Lederkremer, R.M. Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration |
| topic_facet |
carbohydrate derivative sugar article chemical structure nuclear magnetic resonance synthesis |
| description |
Methyl 2,3-di-O-benzoyl-6-deoxy-4-O-(p-tolylsulfonyl) and 4-O-[(p-nitrophenyl)sulfonyl]-α-d-mannopyranosides (9 and 10) were prepared by three different routes from methyl α-d-mannopyranoside (1). The analogous 4-sulfonyloxy derivatives having HO-2 and HO-3 free (14 and 15) were also synthesized from 1. Nucleophilic substitution of the sulfonyloxy group of 9, 10, 14, and 15 by potassium thiocyanate in N,N-dimethylformamide was attempted. Compounds 9 and 10 gave a mixture of solvolysis products: methyl 2,3-di-O-benzoyl-6-deoxy-α-d-talopyranoside (17), methyl 3,4-di-O-benzoyl-6-deoxy-α-d-talopyranoside (18), and methyl 2,4-di-O-benzoyl-6-deoxy-α-d-talopyranoside (19), which are evidently formed by intramolecular displacement of the 4-sulfonate by backside attack of the C-2 benzoyloxy substituent, followed by benzoyl migration. The structure of compounds 17-19 was established by spectroscopic analysis, and then chemically confirmed. Although compound 14 decomposed during the substitution reaction, the 4-p-nitrophenylsulfonyl derivative 15 gave a 2:1 mixture of the 4-thiocyano derivatives with inversion [methyl 4,6-dideoxy-4-thiocyano-α-d-talopyranoside (22)] and retention [methyl 4,6-dideoxy-4-thiocyano-α-d-mannopyranoside (23)] of the C-4 configuration. © 1991. |
| format |
JOUR |
| author |
Cicero, D. Varela, O. De Lederkremer, R.M. |
| author_facet |
Cicero, D. Varela, O. De Lederkremer, R.M. |
| author_sort |
Cicero, D. |
| title |
Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration |
| title_short |
Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration |
| title_full |
Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration |
| title_fullStr |
Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration |
| title_full_unstemmed |
Nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration |
| title_sort |
nucleophilic displacement-reactions of the 4-sulfonyloxy group in derivatives having the d-manno configuration |
| url |
http://hdl.handle.net/20.500.12110/paper_00086215_v211_n2_p295_Cicero |
| work_keys_str_mv |
AT cicerod nucleophilicdisplacementreactionsofthe4sulfonyloxygroupinderivativeshavingthedmannoconfiguration AT varelao nucleophilicdisplacementreactionsofthe4sulfonyloxygroupinderivativeshavingthedmannoconfiguration AT delederkremerrm nucleophilicdisplacementreactionsofthe4sulfonyloxygroupinderivativeshavingthedmannoconfiguration |
| _version_ |
1807316057196593152 |