Comprehensive reinvestigation of the reaction of D-aldoses with meldrum's acid yielding mainly chain extended 3,6-anhydro-2-deoxy-aldono-1,4-lactones

Peter Köll, Angelika Wernicke, J. Kovács, Arne Lützen

Research output: Article

14 Citations (Scopus)

Abstract

All diastereomeric aldo-D-pentoses and -D-hexoses were reacted with Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) under basic conditions. A protocol was applied and optimized which was originally reported by J. A. Galbis Perez et al. in 1990. In every case formal substitution of the anomeric hydroxyl against a carboxy-methylene group occurred thus elongating the carbon chain of the parent aldose by a C2 fragment. Products are mainly 3,6-anhydro-2-deoxy-aldono-1,4-lactones in which the lactone rings are annulated to a furanoid system. However, D-mannose and D-lyxose also gave pyranoid 3,7-anhydro-1,4-lactones. Intermediates are unsaturated open-chain 1,4-lactones (butenolides) which in some cases could be isolated as by-products. Epimerisation at C-2 of the parent aldose occurred at least partially in most reactions. The products and their acetylated derivatives were characterized by 1H and 13C NMR spectroscopy. A proposed mechanism of this reaction is supported by additional experimental evidence.

Original languageEnglish
Pages (from-to)1019-1047
Number of pages29
JournalJournal of Carbohydrate Chemistry
Volume19
Issue number8
Publication statusPublished - 2000

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Lactones
Pentoses
Hexoses
Mannose
Hydroxyl Radical
Nuclear magnetic resonance spectroscopy
Byproducts
Substitution reactions
Magnetic Resonance Spectroscopy
Carbon
Derivatives
Meldrum's acid

ASJC Scopus subject areas

  • Biochemistry, Genetics and Molecular Biology(all)
  • Biochemistry
  • Organic Chemistry

Cite this

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title = "Comprehensive reinvestigation of the reaction of D-aldoses with meldrum's acid yielding mainly chain extended 3,6-anhydro-2-deoxy-aldono-1,4-lactones",
abstract = "All diastereomeric aldo-D-pentoses and -D-hexoses were reacted with Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) under basic conditions. A protocol was applied and optimized which was originally reported by J. A. Galbis Perez et al. in 1990. In every case formal substitution of the anomeric hydroxyl against a carboxy-methylene group occurred thus elongating the carbon chain of the parent aldose by a C2 fragment. Products are mainly 3,6-anhydro-2-deoxy-aldono-1,4-lactones in which the lactone rings are annulated to a furanoid system. However, D-mannose and D-lyxose also gave pyranoid 3,7-anhydro-1,4-lactones. Intermediates are unsaturated open-chain 1,4-lactones (butenolides) which in some cases could be isolated as by-products. Epimerisation at C-2 of the parent aldose occurred at least partially in most reactions. The products and their acetylated derivatives were characterized by 1H and 13C NMR spectroscopy. A proposed mechanism of this reaction is supported by additional experimental evidence.",
author = "Peter K{\"o}ll and Angelika Wernicke and J. Kov{\'a}cs and Arne L{\"u}tzen",
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journal = "Journal of Carbohydrate Chemistry",
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AU - Köll, Peter

AU - Wernicke, Angelika

AU - Kovács, J.

AU - Lützen, Arne

PY - 2000

Y1 - 2000

N2 - All diastereomeric aldo-D-pentoses and -D-hexoses were reacted with Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) under basic conditions. A protocol was applied and optimized which was originally reported by J. A. Galbis Perez et al. in 1990. In every case formal substitution of the anomeric hydroxyl against a carboxy-methylene group occurred thus elongating the carbon chain of the parent aldose by a C2 fragment. Products are mainly 3,6-anhydro-2-deoxy-aldono-1,4-lactones in which the lactone rings are annulated to a furanoid system. However, D-mannose and D-lyxose also gave pyranoid 3,7-anhydro-1,4-lactones. Intermediates are unsaturated open-chain 1,4-lactones (butenolides) which in some cases could be isolated as by-products. Epimerisation at C-2 of the parent aldose occurred at least partially in most reactions. The products and their acetylated derivatives were characterized by 1H and 13C NMR spectroscopy. A proposed mechanism of this reaction is supported by additional experimental evidence.

AB - All diastereomeric aldo-D-pentoses and -D-hexoses were reacted with Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) under basic conditions. A protocol was applied and optimized which was originally reported by J. A. Galbis Perez et al. in 1990. In every case formal substitution of the anomeric hydroxyl against a carboxy-methylene group occurred thus elongating the carbon chain of the parent aldose by a C2 fragment. Products are mainly 3,6-anhydro-2-deoxy-aldono-1,4-lactones in which the lactone rings are annulated to a furanoid system. However, D-mannose and D-lyxose also gave pyranoid 3,7-anhydro-1,4-lactones. Intermediates are unsaturated open-chain 1,4-lactones (butenolides) which in some cases could be isolated as by-products. Epimerisation at C-2 of the parent aldose occurred at least partially in most reactions. The products and their acetylated derivatives were characterized by 1H and 13C NMR spectroscopy. A proposed mechanism of this reaction is supported by additional experimental evidence.

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