Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid
Acetylation of 2-amino-2-deoxy-d-gluconic acid (1) with acetyl chloride-pyridine gave 2,3-unsaturated six- and five-membered lactones (2 and 3). Their benzoylated analogs (4 and 5) were obtained by benzoylation of 1 with benzoyl chloride-pyridine. Reaction of 1 with hot acetic anhydride-sodium aceta...
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todo:paper_00086215_v193_nC_p49_Horton2023-10-03T14:06:31Z Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid Horton, D. Thomson, J.K. Varela, O. Nin, A. de Lederkremer, R.M. benzenecarbonyl chloride benzoic acid derivative drug derivative glucosamine glucosaminic acid lactone acetylation article chemical structure nuclear magnetic resonance spectroscopy stereoisomerism synthesis Acetylation Benzoates Glucosamine Lactones Magnetic Resonance Spectroscopy Molecular Structure Stereoisomerism Support, Non-U.S. Gov't Support, U.S. Gov't, P.H.S. Acetylation of 2-amino-2-deoxy-d-gluconic acid (1) with acetyl chloride-pyridine gave 2,3-unsaturated six- and five-membered lactones (2 and 3). Their benzoylated analogs (4 and 5) were obtained by benzoylation of 1 with benzoyl chloride-pyridine. Reaction of 1 with hot acetic anhydride-sodium acetate gave a ∼1:2 mixture of (E)- and (Z)-2-acetamido-6-acetoxyhexa-2,4-dien-4-olide (6-E and 6-Z). Treatment of 3 with 1,8-diazabicyclo[5.4.0]undec-7-ene also gave as the main product 6-Z, which was isolated crystalline from the reaction mixture. The same reaction applied to compound 5 gave selectively the Z-isomer of the benzoylated furanone 7. Partial and total hydrogenation (H2PdC) of the mixture 6-E,Z gave, respectively, a racemic monounsaturated lactone (8) and a dideoxy lactone (9), for which the threo-configuration for the chiral centers at C-2 and C-4 was determined. Acidic removal of the acetyl groups from 9 afforded the 2-amino-6-hydroxy-1,4-lactone hydrochloride 10. On the other hand, acetylation at high temperature of the 4,6-O-benzylidene derivative of 1 (11) gave the 2,3-unsaturated, six-membered lactone (12), precursor of 2-acetamido-6-acetoxyhexa-2,4-dien-5-olide (14). © 1989. Fil:Varela, O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Nin, A. 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_v193_nC_p49_Horton |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
benzenecarbonyl chloride benzoic acid derivative drug derivative glucosamine glucosaminic acid lactone acetylation article chemical structure nuclear magnetic resonance spectroscopy stereoisomerism synthesis Acetylation Benzoates Glucosamine Lactones Magnetic Resonance Spectroscopy Molecular Structure Stereoisomerism Support, Non-U.S. Gov't Support, U.S. Gov't, P.H.S. |
| spellingShingle |
benzenecarbonyl chloride benzoic acid derivative drug derivative glucosamine glucosaminic acid lactone acetylation article chemical structure nuclear magnetic resonance spectroscopy stereoisomerism synthesis Acetylation Benzoates Glucosamine Lactones Magnetic Resonance Spectroscopy Molecular Structure Stereoisomerism Support, Non-U.S. Gov't Support, U.S. Gov't, P.H.S. Horton, D. Thomson, J.K. Varela, O. Nin, A. de Lederkremer, R.M. Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid |
| topic_facet |
benzenecarbonyl chloride benzoic acid derivative drug derivative glucosamine glucosaminic acid lactone acetylation article chemical structure nuclear magnetic resonance spectroscopy stereoisomerism synthesis Acetylation Benzoates Glucosamine Lactones Magnetic Resonance Spectroscopy Molecular Structure Stereoisomerism Support, Non-U.S. Gov't Support, U.S. Gov't, P.H.S. |
| description |
Acetylation of 2-amino-2-deoxy-d-gluconic acid (1) with acetyl chloride-pyridine gave 2,3-unsaturated six- and five-membered lactones (2 and 3). Their benzoylated analogs (4 and 5) were obtained by benzoylation of 1 with benzoyl chloride-pyridine. Reaction of 1 with hot acetic anhydride-sodium acetate gave a ∼1:2 mixture of (E)- and (Z)-2-acetamido-6-acetoxyhexa-2,4-dien-4-olide (6-E and 6-Z). Treatment of 3 with 1,8-diazabicyclo[5.4.0]undec-7-ene also gave as the main product 6-Z, which was isolated crystalline from the reaction mixture. The same reaction applied to compound 5 gave selectively the Z-isomer of the benzoylated furanone 7. Partial and total hydrogenation (H2PdC) of the mixture 6-E,Z gave, respectively, a racemic monounsaturated lactone (8) and a dideoxy lactone (9), for which the threo-configuration for the chiral centers at C-2 and C-4 was determined. Acidic removal of the acetyl groups from 9 afforded the 2-amino-6-hydroxy-1,4-lactone hydrochloride 10. On the other hand, acetylation at high temperature of the 4,6-O-benzylidene derivative of 1 (11) gave the 2,3-unsaturated, six-membered lactone (12), precursor of 2-acetamido-6-acetoxyhexa-2,4-dien-5-olide (14). © 1989. |
| format |
JOUR |
| author |
Horton, D. Thomson, J.K. Varela, O. Nin, A. de Lederkremer, R.M. |
| author_facet |
Horton, D. Thomson, J.K. Varela, O. Nin, A. de Lederkremer, R.M. |
| author_sort |
Horton, D. |
| title |
Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid |
| title_short |
Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid |
| title_full |
Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid |
| title_fullStr |
Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid |
| title_full_unstemmed |
Confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid |
| title_sort |
confirmation of the structures of the products obtained on acylation of 2-amino-2-deoxy-d-gluconic acid |
| url |
http://hdl.handle.net/20.500.12110/paper_00086215_v193_nC_p49_Horton |
| work_keys_str_mv |
AT hortond confirmationofthestructuresoftheproductsobtainedonacylationof2amino2deoxydgluconicacid AT thomsonjk confirmationofthestructuresoftheproductsobtainedonacylationof2amino2deoxydgluconicacid AT varelao confirmationofthestructuresoftheproductsobtainedonacylationof2amino2deoxydgluconicacid AT nina confirmationofthestructuresoftheproductsobtainedonacylationof2amino2deoxydgluconicacid AT delederkremerrm confirmationofthestructuresoftheproductsobtainedonacylationof2amino2deoxydgluconicacid |
| _version_ |
1807321461776449536 |