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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todo:paper_00223263_v61_n12_p4007_DiNardo2023-10-03T14:31:20Z A carbohydrate approach to the enantioselective synthesis of 1,3-polyols Di Nardo, C. Jeroncic, L.O. De Lederkremer, R.M. Varela, O. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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. |
format |
JOUR |
author |
Di Nardo, C. Jeroncic, L.O. De Lederkremer, R.M. Varela, O. |
spellingShingle |
Di Nardo, C. Jeroncic, L.O. De Lederkremer, R.M. Varela, O. A carbohydrate approach to the enantioselective synthesis of 1,3-polyols |
author_facet |
Di Nardo, C. Jeroncic, L.O. De Lederkremer, R.M. Varela, O. |
author_sort |
Di Nardo, C. |
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 |
url |
http://hdl.handle.net/20.500.12110/paper_00223263_v61_n12_p4007_DiNardo |
work_keys_str_mv |
AT dinardoc acarbohydrateapproachtotheenantioselectivesynthesisof13polyols AT jeronciclo acarbohydrateapproachtotheenantioselectivesynthesisof13polyols AT delederkremerrm acarbohydrateapproachtotheenantioselectivesynthesisof13polyols AT varelao acarbohydrateapproachtotheenantioselectivesynthesisof13polyols AT dinardoc carbohydrateapproachtotheenantioselectivesynthesisof13polyols AT jeronciclo carbohydrateapproachtotheenantioselectivesynthesisof13polyols AT delederkremerrm carbohydrateapproachtotheenantioselectivesynthesisof13polyols AT varelao carbohydrateapproachtotheenantioselectivesynthesisof13polyols |
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1807319502083325952 |