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, C., Jeroncic, L.O., De Lederkremer, R.M., Varela, O.
Formato:	JOUR
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_00223263_v61_n12_p4007_DiNardo
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_00223263_v61_n12_p4007_DiNardo
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spelling	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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A carbohydrate approach to the enantioselective synthesis of 1,3-polyols

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