Synthesis of 6-deoxy-6-phenylphosphonoyl-D-fructopyranoses: The first phosphorus-in-the-ring analogues of a ketose

Tadashi Hanaya, Ryuji Okamoto, Yurij V. Prikhod'ko, Margaret Ann Armour, Alan M. Hogg, Hiroshi Yamamoto

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Abstract

The title sugar analogues were synthesized through three routes, by starting with three kinds of 6-O-tosyl-D-fructofuranoses. (i) Treatment of the known 2,3-O-isopropylidene-1,6-di-O-tosyl-β-D-fructofuranose successively with methyl iodide-silver oxide, sodium iodide and diethyl phenylphosphonite provided 6-deoxy-6-[(ethoxy)phenylphosphinoyl]-2,3-O-isopropylidene-4-O-methyl-1-O-tosyl- β-D-fructofuranose in 67% overall yield. This was reduced with sodium dihydrobis-(2-methoxyethoxy)aluminate, followed by hydrolysis with acid, to afford a mixture of the 4-O-methyl-1-O-tosyl and 1-deoxy-4-O-methyl derivatives of the title compound. (ii) Treatment of D-fructose with 2-methoxypropene in the presence of TsOH and then with TsCl in pyridine afforded 1,3-O-isopropylidene-6-O-tosyl-α-D-fructofuranose (35% yield). This was subjected to the same five-step conversion, to give the 4-O-methyl derivatives of the title compound. (iii) Treatment of D-fructose with 2,2-dimethoxypropane-SnCl2 and then with TsCl-pyridine gave 1,2-O-isopropylidene-6-O-tosyl-β-D-fructofuranose (23% yield). This was elaborated, in three steps, to either the 3,4-di-O-acetyl-6-deoxy-6-[(ethoxy)phenylphosphinoyl] derivative (84% yield) or the 3,4-bis-O-(tetrahydropyran-2-yl) congener (54% yield), both of which furnished, in two steps, the unsubstituted title compound. The products obtained in the three approaches (i-iii) were converted into the corresponding per-O-acetates, whose structures and conformations [2C5(D), 5C2(D), or B3,6] were established by spectroscopy.

Original languageEnglish
Pages (from-to)1663-1671
Number of pages9
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number14
Publication statusPublished - 1993

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Ketoses
Phosphorus
Fructose
Derivatives
Sodium Iodide
Sugars
Conformations
Hydrolysis
Acetates
Sodium
Spectroscopy
Acids
propylene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis of 6-deoxy-6-phenylphosphonoyl-D-fructopyranoses : The first phosphorus-in-the-ring analogues of a ketose. / Hanaya, Tadashi; Okamoto, Ryuji; Prikhod'ko, Yurij V.; Armour, Margaret Ann; Hogg, Alan M.; Yamamoto, Hiroshi.

In: Journal of the Chemical Society, Perkin Transactions 1, No. 14, 1993, p. 1663-1671.

Research output: Contribution to journalArticle

Hanaya, Tadashi ; Okamoto, Ryuji ; Prikhod'ko, Yurij V. ; Armour, Margaret Ann ; Hogg, Alan M. ; Yamamoto, Hiroshi. / Synthesis of 6-deoxy-6-phenylphosphonoyl-D-fructopyranoses : The first phosphorus-in-the-ring analogues of a ketose. In: Journal of the Chemical Society, Perkin Transactions 1. 1993 ; No. 14. pp. 1663-1671.
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abstract = "The title sugar analogues were synthesized through three routes, by starting with three kinds of 6-O-tosyl-D-fructofuranoses. (i) Treatment of the known 2,3-O-isopropylidene-1,6-di-O-tosyl-β-D-fructofuranose successively with methyl iodide-silver oxide, sodium iodide and diethyl phenylphosphonite provided 6-deoxy-6-[(ethoxy)phenylphosphinoyl]-2,3-O-isopropylidene-4-O-methyl-1-O-tosyl- β-D-fructofuranose in 67{\%} overall yield. This was reduced with sodium dihydrobis-(2-methoxyethoxy)aluminate, followed by hydrolysis with acid, to afford a mixture of the 4-O-methyl-1-O-tosyl and 1-deoxy-4-O-methyl derivatives of the title compound. (ii) Treatment of D-fructose with 2-methoxypropene in the presence of TsOH and then with TsCl in pyridine afforded 1,3-O-isopropylidene-6-O-tosyl-α-D-fructofuranose (35{\%} yield). This was subjected to the same five-step conversion, to give the 4-O-methyl derivatives of the title compound. (iii) Treatment of D-fructose with 2,2-dimethoxypropane-SnCl2 and then with TsCl-pyridine gave 1,2-O-isopropylidene-6-O-tosyl-β-D-fructofuranose (23{\%} yield). This was elaborated, in three steps, to either the 3,4-di-O-acetyl-6-deoxy-6-[(ethoxy)phenylphosphinoyl] derivative (84{\%} yield) or the 3,4-bis-O-(tetrahydropyran-2-yl) congener (54{\%} yield), both of which furnished, in two steps, the unsubstituted title compound. The products obtained in the three approaches (i-iii) were converted into the corresponding per-O-acetates, whose structures and conformations [2C5(D), 5C2(D), or B3,6] were established by spectroscopy.",
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T2 - The first phosphorus-in-the-ring analogues of a ketose

AU - Hanaya, Tadashi

AU - Okamoto, Ryuji

AU - Prikhod'ko, Yurij V.

AU - Armour, Margaret Ann

AU - Hogg, Alan M.

AU - Yamamoto, Hiroshi

PY - 1993

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N2 - The title sugar analogues were synthesized through three routes, by starting with three kinds of 6-O-tosyl-D-fructofuranoses. (i) Treatment of the known 2,3-O-isopropylidene-1,6-di-O-tosyl-β-D-fructofuranose successively with methyl iodide-silver oxide, sodium iodide and diethyl phenylphosphonite provided 6-deoxy-6-[(ethoxy)phenylphosphinoyl]-2,3-O-isopropylidene-4-O-methyl-1-O-tosyl- β-D-fructofuranose in 67% overall yield. This was reduced with sodium dihydrobis-(2-methoxyethoxy)aluminate, followed by hydrolysis with acid, to afford a mixture of the 4-O-methyl-1-O-tosyl and 1-deoxy-4-O-methyl derivatives of the title compound. (ii) Treatment of D-fructose with 2-methoxypropene in the presence of TsOH and then with TsCl in pyridine afforded 1,3-O-isopropylidene-6-O-tosyl-α-D-fructofuranose (35% yield). This was subjected to the same five-step conversion, to give the 4-O-methyl derivatives of the title compound. (iii) Treatment of D-fructose with 2,2-dimethoxypropane-SnCl2 and then with TsCl-pyridine gave 1,2-O-isopropylidene-6-O-tosyl-β-D-fructofuranose (23% yield). This was elaborated, in three steps, to either the 3,4-di-O-acetyl-6-deoxy-6-[(ethoxy)phenylphosphinoyl] derivative (84% yield) or the 3,4-bis-O-(tetrahydropyran-2-yl) congener (54% yield), both of which furnished, in two steps, the unsubstituted title compound. The products obtained in the three approaches (i-iii) were converted into the corresponding per-O-acetates, whose structures and conformations [2C5(D), 5C2(D), or B3,6] were established by spectroscopy.

AB - The title sugar analogues were synthesized through three routes, by starting with three kinds of 6-O-tosyl-D-fructofuranoses. (i) Treatment of the known 2,3-O-isopropylidene-1,6-di-O-tosyl-β-D-fructofuranose successively with methyl iodide-silver oxide, sodium iodide and diethyl phenylphosphonite provided 6-deoxy-6-[(ethoxy)phenylphosphinoyl]-2,3-O-isopropylidene-4-O-methyl-1-O-tosyl- β-D-fructofuranose in 67% overall yield. This was reduced with sodium dihydrobis-(2-methoxyethoxy)aluminate, followed by hydrolysis with acid, to afford a mixture of the 4-O-methyl-1-O-tosyl and 1-deoxy-4-O-methyl derivatives of the title compound. (ii) Treatment of D-fructose with 2-methoxypropene in the presence of TsOH and then with TsCl in pyridine afforded 1,3-O-isopropylidene-6-O-tosyl-α-D-fructofuranose (35% yield). This was subjected to the same five-step conversion, to give the 4-O-methyl derivatives of the title compound. (iii) Treatment of D-fructose with 2,2-dimethoxypropane-SnCl2 and then with TsCl-pyridine gave 1,2-O-isopropylidene-6-O-tosyl-β-D-fructofuranose (23% yield). This was elaborated, in three steps, to either the 3,4-di-O-acetyl-6-deoxy-6-[(ethoxy)phenylphosphinoyl] derivative (84% yield) or the 3,4-bis-O-(tetrahydropyran-2-yl) congener (54% yield), both of which furnished, in two steps, the unsubstituted title compound. The products obtained in the three approaches (i-iii) were converted into the corresponding per-O-acetates, whose structures and conformations [2C5(D), 5C2(D), or B3,6] were established by spectroscopy.

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