Synthesis of 2,4-dideoxy-4-hydroxyphosphonoyl-D-erythro- and -L-threo-pentofuranoses

Tadashi Hanaya, Ayashi Noguchi, Margaret Ann Armour, Alan M. Hogg, Hiroshi Yamamoto

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Abstract

Treatment of 3,5, 6-trideoxy-1,2-O-isopropylidene-6-nitro-α-D- erythro-hex-5-enofuranose with dimethyl phosphonate in the presence of triethylamine, followed by catalytic hydrogenation and then deamination with nitrous acid, provided mainly a 2:1 mixture of 3,5-dideoxy-5- dimethoxyphosphinoyl-1,2-O-isopropylidene-α-D-ribo- and -β-L-lyxo-hexofuranose in 57% overall yield. This mixture was deacetonated, oxidized with sodium periodate, and then treated with acidic methanol to afford methyl 2,4-dideoxy-4-dimethoxyphosphinoyl-α,β-D-erythro- pentopyranosides (41% over-all yield from the aforementioned phosphinoylfuranose) and -L-threo-pentopyranosides (17% overall yield). The major products were reduced with sodium dihydrobis-(2-methoxyethoxy)-aluminate, followed by hydrolysis with acid and then oxidation with hydrogen peroxide, to afford the title D-erythro compounds, whereas similar treatment of the minor pyranosides afforded the corresponding L-threo-pentofuranoses. These compounds were converted into the corresponding 1,3,5-tri-O-acetyl-5-methoxyphosphonoyl derivatives, whose structures and conformations [mostly 3T 2(D) for one and 2T3(L) for the other] were established by spectroscopy.

Original languageEnglish
Pages (from-to)295-301
Number of pages7
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number2
Publication statusPublished - 1992

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Nitrous Acid
Hydrogen Peroxide
Hydrogenation
Methanol
Conformations
Hydrolysis
Sodium
Spectroscopy
Derivatives
Oxidation
Acids
propylene
dimethyl hydrogen phosphite
triethylamine
dihydrobis(2-methoxyethoxy)aluminate
metaperiodate

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis of 2,4-dideoxy-4-hydroxyphosphonoyl-D-erythro- and -L-threo-pentofuranoses. / Hanaya, Tadashi; Noguchi, Ayashi; Armour, Margaret Ann; Hogg, Alan M.; Yamamoto, Hiroshi.

In: Journal of the Chemical Society, Perkin Transactions 1, No. 2, 1992, p. 295-301.

Research output: Contribution to journalArticle

Hanaya, Tadashi ; Noguchi, Ayashi ; Armour, Margaret Ann ; Hogg, Alan M. ; Yamamoto, Hiroshi. / Synthesis of 2,4-dideoxy-4-hydroxyphosphonoyl-D-erythro- and -L-threo-pentofuranoses. In: Journal of the Chemical Society, Perkin Transactions 1. 1992 ; No. 2. pp. 295-301.
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abstract = "Treatment of 3,5, 6-trideoxy-1,2-O-isopropylidene-6-nitro-α-D- erythro-hex-5-enofuranose with dimethyl phosphonate in the presence of triethylamine, followed by catalytic hydrogenation and then deamination with nitrous acid, provided mainly a 2:1 mixture of 3,5-dideoxy-5- dimethoxyphosphinoyl-1,2-O-isopropylidene-α-D-ribo- and -β-L-lyxo-hexofuranose in 57{\%} overall yield. This mixture was deacetonated, oxidized with sodium periodate, and then treated with acidic methanol to afford methyl 2,4-dideoxy-4-dimethoxyphosphinoyl-α,β-D-erythro- pentopyranosides (41{\%} over-all yield from the aforementioned phosphinoylfuranose) and -L-threo-pentopyranosides (17{\%} overall yield). The major products were reduced with sodium dihydrobis-(2-methoxyethoxy)-aluminate, followed by hydrolysis with acid and then oxidation with hydrogen peroxide, to afford the title D-erythro compounds, whereas similar treatment of the minor pyranosides afforded the corresponding L-threo-pentofuranoses. These compounds were converted into the corresponding 1,3,5-tri-O-acetyl-5-methoxyphosphonoyl derivatives, whose structures and conformations [mostly 3T 2(D) for one and 2T3(L) for the other] were established by spectroscopy.",
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