A carbohydrate approach to the enantioselective synthesis of 1,3-polyols

Treatment of per-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone (2) with tertiary amines afforded selectively and with good yields the (5H)-furan-2-one derivatives 3, 4, and 5, formed by controlled elimination of one, two, or three molecules of benzoic acid, respectively. The stereochemistry for the...

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Autores principales: Di Nardo, Christián Esteban, Jeroncic, Lucio Orlando, Muchnik de Lederkremer, Rosa María, Varela, Oscar José
Publicado: 1996
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v61_n12_p4007_DiNardo
http://hdl.handle.net/20.500.12110/paper_00223263_v61_n12_p4007_DiNardo
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_00223263_v61_n12_p4007_DiNardo2023-06-08T14:49:29Z A carbohydrate approach to the enantioselective synthesis of 1,3-polyols Di Nardo, Christián Esteban Jeroncic, Lucio Orlando Muchnik de Lederkremer, Rosa María Varela, Oscar José Treatment of per-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone (2) with tertiary amines afforded selectively and with good yields the (5H)-furan-2-one derivatives 3, 4, and 5, formed by controlled elimination of one, two, or three molecules of benzoic acid, respectively. The stereochemistry for the exocyclic double bonds of 4 and 5 was determined by means of NMR techniques. Particularly, the furanone 4 was obtained from 2 (∼90% yield) as a mixture of the E and Z diastereoisomers, which were separated by column chromatography or, more efficiently, by HPLC. The catalytic hydrogenation of compounds 4-E and 4-Z took place diastereoselectively, due to the chiral induction of the stereocenter located in the lateral chain. Thus, hydrogenation of 4-E led to a mixture of the 4,5-dihydro-(3H)-furan-2-ones having 3R,5S,2′S (D-xylo, 6) and 3S,5R,2′S (D-arabino, 7) configurations, with 6 as the major product; whereas the 4-Z isomer gave the same mixture, but being 7 preponderant. On hydrogenation of the original 4-E / Z mixture, compound 6 was obtained pure after recrystallization. O-Debenzoylation of 6 gave 9, which was reduced with NaBH4 to the 3,5-dideoxy-meso-xylo-heptitol (11). The peracetate (12) and perbenzoate (13) of the latter were prepared, and the 1-(tert-butyldiphenylsilyl)oxy derivative (16) was also synthesized via the 3′-(silyloxy)-4,5-dihydro-(3H)-furan-2-one 14. Chemoselective reduction of the lactone function of 6 with diisoamylborane gave the 2,5,6-tri-O-benzoyl-3,6-dideoxy-D-xylo-heptofuranose (17). The 3,5-dideoxy-D-arabino-heptitol (18), a diastereoisomer of 11, was also isolated and characterized. Fil:Di Nardo, C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Jeroncic, L.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. Fil:Varela, O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1996 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v61_n12_p4007_DiNardo http://hdl.handle.net/20.500.12110/paper_00223263_v61_n12_p4007_DiNardo
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description Treatment of per-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone (2) with tertiary amines afforded selectively and with good yields the (5H)-furan-2-one derivatives 3, 4, and 5, formed by controlled elimination of one, two, or three molecules of benzoic acid, respectively. The stereochemistry for the exocyclic double bonds of 4 and 5 was determined by means of NMR techniques. Particularly, the furanone 4 was obtained from 2 (∼90% yield) as a mixture of the E and Z diastereoisomers, which were separated by column chromatography or, more efficiently, by HPLC. The catalytic hydrogenation of compounds 4-E and 4-Z took place diastereoselectively, due to the chiral induction of the stereocenter located in the lateral chain. Thus, hydrogenation of 4-E led to a mixture of the 4,5-dihydro-(3H)-furan-2-ones having 3R,5S,2′S (D-xylo, 6) and 3S,5R,2′S (D-arabino, 7) configurations, with 6 as the major product; whereas the 4-Z isomer gave the same mixture, but being 7 preponderant. On hydrogenation of the original 4-E / Z mixture, compound 6 was obtained pure after recrystallization. O-Debenzoylation of 6 gave 9, which was reduced with NaBH4 to the 3,5-dideoxy-meso-xylo-heptitol (11). The peracetate (12) and perbenzoate (13) of the latter were prepared, and the 1-(tert-butyldiphenylsilyl)oxy derivative (16) was also synthesized via the 3′-(silyloxy)-4,5-dihydro-(3H)-furan-2-one 14. Chemoselective reduction of the lactone function of 6 with diisoamylborane gave the 2,5,6-tri-O-benzoyl-3,6-dideoxy-D-xylo-heptofuranose (17). The 3,5-dideoxy-D-arabino-heptitol (18), a diastereoisomer of 11, was also isolated and characterized.
author Di Nardo, Christián Esteban
Jeroncic, Lucio Orlando
Muchnik de Lederkremer, Rosa María
Varela, Oscar José
spellingShingle Di Nardo, Christián Esteban
Jeroncic, Lucio Orlando
Muchnik de Lederkremer, Rosa María
Varela, Oscar José
A carbohydrate approach to the enantioselective synthesis of 1,3-polyols
author_facet Di Nardo, Christián Esteban
Jeroncic, Lucio Orlando
Muchnik de Lederkremer, Rosa María
Varela, Oscar José
author_sort Di Nardo, Christián Esteban
title A carbohydrate approach to the enantioselective synthesis of 1,3-polyols
title_short A carbohydrate approach to the enantioselective synthesis of 1,3-polyols
title_full A carbohydrate approach to the enantioselective synthesis of 1,3-polyols
title_fullStr A carbohydrate approach to the enantioselective synthesis of 1,3-polyols
title_full_unstemmed A carbohydrate approach to the enantioselective synthesis of 1,3-polyols
title_sort carbohydrate approach to the enantioselective synthesis of 1,3-polyols
publishDate 1996
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v61_n12_p4007_DiNardo
http://hdl.handle.net/20.500.12110/paper_00223263_v61_n12_p4007_DiNardo
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