The isopropylidenation of d-ribose diethyl dithioacetal and ribitol. A new synthesis of α- and β-d-ribofuranosylethyne via 2,3

4,5-di-O-isopropylidene-aldehydo-d-ribose

Gaffar Aslani-Shotorbani, J. Grant Buchanan, Alan R. Edgar, Parvin K. Shahidi

Research output: Contribution to journalArticle

Abstract

The reaction of d-ribose diethyl dithioacetal with acetone and sulphuric acid in the presence of anhydrous copper sulphate gives the 2,3:4,5-di-O-isopropylidene derivative 14 (40%) and the isomeric 2,5:3,4-di-O-isopropylidene acetal 17 (40%), contrary to the conclusions of some previous investigators. Earlier work on the structures of the mono-O-isopropylidene derivatives formed when copper sulphate alone is the catalyst has been confirmed and extended. The diacetonides 14 and 17 were converted into the aldehydo-d-ribose derivatives 11 and 30, respectively, and thence into the di-O-isopropylideneribitol derivatives 24 and 25. When ribitol was treated with acetone and sulphuric acid, 1,2:4,5-di-O-isopropylideneribitol (66%) was the major product, together with dl-24 (22%) and dl-25 (11%). The aldehydo-d-ribose 11 reacted with ethynylmagnesium bromide in tetrahydrofuran to give the d-altro and d-allo alcohols 39 and 40 in the ratio 2:1. Toluene-p-sulphonylation of the mixture of 39 and 40, followed by solvolysis in buffered, boiling aqueous ethanol, afforded the 2,3-O-isopropylidene-d-ribofuranosylethynes 45 and 46 with loss of the terminal O-isopropylidene group. 13C-N.m.r. spectroscopy was used extensively to determine the ring sizes of the isopropylidene derivatives. © 1985.

Original languageEnglish
Pages (from-to)37-52
Number of pages16
JournalCarbohydrate Research
Volume136
Issue numberC
Publication statusPublished - 28 Feb 1985

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Ribitol
Ribose
Derivatives
Copper Sulfate
Acetone
Acetals
Acids
Toluene
Bromides
Boiling liquids
propylene
Ethanol
Alcohols
Spectroscopy
Catalysts

Cite this

Aslani-Shotorbani, Gaffar ; Buchanan, J. Grant ; Edgar, Alan R. ; Shahidi, Parvin K. / The isopropylidenation of d-ribose diethyl dithioacetal and ribitol. A new synthesis of α- and β-d-ribofuranosylethyne via 2,3 : 4,5-di-O-isopropylidene-aldehydo-d-ribose. In: Carbohydrate Research. 1985 ; Vol. 136, No. C. pp. 37-52.
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abstract = "The reaction of d-ribose diethyl dithioacetal with acetone and sulphuric acid in the presence of anhydrous copper sulphate gives the 2,3:4,5-di-O-isopropylidene derivative 14 (40{\%}) and the isomeric 2,5:3,4-di-O-isopropylidene acetal 17 (40{\%}), contrary to the conclusions of some previous investigators. Earlier work on the structures of the mono-O-isopropylidene derivatives formed when copper sulphate alone is the catalyst has been confirmed and extended. The diacetonides 14 and 17 were converted into the aldehydo-d-ribose derivatives 11 and 30, respectively, and thence into the di-O-isopropylideneribitol derivatives 24 and 25. When ribitol was treated with acetone and sulphuric acid, 1,2:4,5-di-O-isopropylideneribitol (66{\%}) was the major product, together with dl-24 (22{\%}) and dl-25 (11{\%}). The aldehydo-d-ribose 11 reacted with ethynylmagnesium bromide in tetrahydrofuran to give the d-altro and d-allo alcohols 39 and 40 in the ratio 2:1. Toluene-p-sulphonylation of the mixture of 39 and 40, followed by solvolysis in buffered, boiling aqueous ethanol, afforded the 2,3-O-isopropylidene-d-ribofuranosylethynes 45 and 46 with loss of the terminal O-isopropylidene group. 13C-N.m.r. spectroscopy was used extensively to determine the ring sizes of the isopropylidene derivatives. {\circledC} 1985.",
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The isopropylidenation of d-ribose diethyl dithioacetal and ribitol. A new synthesis of α- and β-d-ribofuranosylethyne via 2,3 : 4,5-di-O-isopropylidene-aldehydo-d-ribose. / Aslani-Shotorbani, Gaffar; Buchanan, J. Grant; Edgar, Alan R.; Shahidi, Parvin K.

In: Carbohydrate Research, Vol. 136, No. C, 28.02.1985, p. 37-52.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The isopropylidenation of d-ribose diethyl dithioacetal and ribitol. A new synthesis of α- and β-d-ribofuranosylethyne via 2,3

T2 - 4,5-di-O-isopropylidene-aldehydo-d-ribose

AU - Aslani-Shotorbani, Gaffar

AU - Buchanan, J. Grant

AU - Edgar, Alan R.

AU - Shahidi, Parvin K.

PY - 1985/2/28

Y1 - 1985/2/28

N2 - The reaction of d-ribose diethyl dithioacetal with acetone and sulphuric acid in the presence of anhydrous copper sulphate gives the 2,3:4,5-di-O-isopropylidene derivative 14 (40%) and the isomeric 2,5:3,4-di-O-isopropylidene acetal 17 (40%), contrary to the conclusions of some previous investigators. Earlier work on the structures of the mono-O-isopropylidene derivatives formed when copper sulphate alone is the catalyst has been confirmed and extended. The diacetonides 14 and 17 were converted into the aldehydo-d-ribose derivatives 11 and 30, respectively, and thence into the di-O-isopropylideneribitol derivatives 24 and 25. When ribitol was treated with acetone and sulphuric acid, 1,2:4,5-di-O-isopropylideneribitol (66%) was the major product, together with dl-24 (22%) and dl-25 (11%). The aldehydo-d-ribose 11 reacted with ethynylmagnesium bromide in tetrahydrofuran to give the d-altro and d-allo alcohols 39 and 40 in the ratio 2:1. Toluene-p-sulphonylation of the mixture of 39 and 40, followed by solvolysis in buffered, boiling aqueous ethanol, afforded the 2,3-O-isopropylidene-d-ribofuranosylethynes 45 and 46 with loss of the terminal O-isopropylidene group. 13C-N.m.r. spectroscopy was used extensively to determine the ring sizes of the isopropylidene derivatives. © 1985.

AB - The reaction of d-ribose diethyl dithioacetal with acetone and sulphuric acid in the presence of anhydrous copper sulphate gives the 2,3:4,5-di-O-isopropylidene derivative 14 (40%) and the isomeric 2,5:3,4-di-O-isopropylidene acetal 17 (40%), contrary to the conclusions of some previous investigators. Earlier work on the structures of the mono-O-isopropylidene derivatives formed when copper sulphate alone is the catalyst has been confirmed and extended. The diacetonides 14 and 17 were converted into the aldehydo-d-ribose derivatives 11 and 30, respectively, and thence into the di-O-isopropylideneribitol derivatives 24 and 25. When ribitol was treated with acetone and sulphuric acid, 1,2:4,5-di-O-isopropylideneribitol (66%) was the major product, together with dl-24 (22%) and dl-25 (11%). The aldehydo-d-ribose 11 reacted with ethynylmagnesium bromide in tetrahydrofuran to give the d-altro and d-allo alcohols 39 and 40 in the ratio 2:1. Toluene-p-sulphonylation of the mixture of 39 and 40, followed by solvolysis in buffered, boiling aqueous ethanol, afforded the 2,3-O-isopropylidene-d-ribofuranosylethynes 45 and 46 with loss of the terminal O-isopropylidene group. 13C-N.m.r. spectroscopy was used extensively to determine the ring sizes of the isopropylidene derivatives. © 1985.

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JF - Carbohydrate Research

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