C-nucleoside studies. Part 17. The synthesis of 3(5)-carbamoyl-5(3)-β- D ribofuranosylpyrazole (4-deoxypyrazofurin) and 4-amino-3(5)-carbamoyl-5(3)- β-D-ribofuranosylpyrazole

J. Grant Buchanan, Naveen K. Saxena, Richard H. Wightman

Research output: Contribution to journalArticle

Abstract

4-Amino-3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-ß-D-ribofuranosyl)pyrazole (10) was converted into the diazopyrazole (11) by treatment with nitrous acid. On photolysis in aqueous dioxane using visible light compound (11) gave 3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-ß-D-ribofuranosyl)pyrazole (12) [48% from (10)] which formed the corresponding amide (13) (75%) with alkaline hydrogen peroxide. Deprotection of compound (13) with methanolic ammonia afforded 3(5)-carbamoyl-5(3)-ß-D-ribofuranosylpyrazole (4) (74%), the 4-deoxy analogue of pyrazofurin (3). 3(5)-Cyano-4-nitro-5(3)-(2,3,5-tri-O- acetyl-ß-D-ribofuranosyl)pyrazole (1) reacted with dihydropyran and toluene-p-sulphonic acid to give the N-tetrahydropyranyl derivative (21) (66.5%). Hydrolysis of the nitrile group of compound (21), using alkaline hydrogen peroxide, afforded the amide (22) (71%) which was deprotected to give 3(5)-carbamoyl-4-nitro-5(3)-ß-D-ribofuranosylpyrazole (23) (83%). Catalytic reduction of compound (23) gave 4-amino-3(5)-carbamoyl-5(3)-ß-D- ribofuranosylpyrazole (5) (83%) which could be converted into formycin B (24) (69%).

Original languageEnglish
Pages (from-to)2367-2370
Number of pages4
JournalJournal of the Chemical Society, Perkin Transactions 1
Publication statusPublished - 1984

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Nucleosides
pyrazofurin
Amides
Hydrogen Peroxide
Nitrous Acid
Nitriles
Photolysis
Ammonia
Hydrolysis
Derivatives
pyrazole

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@article{89b8c36e55c6460ba3b1ef5420d58819,
title = "C-nucleoside studies. Part 17. The synthesis of 3(5)-carbamoyl-5(3)-β- D ribofuranosylpyrazole (4-deoxypyrazofurin) and 4-amino-3(5)-carbamoyl-5(3)- β-D-ribofuranosylpyrazole",
abstract = "4-Amino-3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-{\ss}-D-ribofuranosyl)pyrazole (10) was converted into the diazopyrazole (11) by treatment with nitrous acid. On photolysis in aqueous dioxane using visible light compound (11) gave 3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-{\ss}-D-ribofuranosyl)pyrazole (12) [48{\%} from (10)] which formed the corresponding amide (13) (75{\%}) with alkaline hydrogen peroxide. Deprotection of compound (13) with methanolic ammonia afforded 3(5)-carbamoyl-5(3)-{\ss}-D-ribofuranosylpyrazole (4) (74{\%}), the 4-deoxy analogue of pyrazofurin (3). 3(5)-Cyano-4-nitro-5(3)-(2,3,5-tri-O- acetyl-{\ss}-D-ribofuranosyl)pyrazole (1) reacted with dihydropyran and toluene-p-sulphonic acid to give the N-tetrahydropyranyl derivative (21) (66.5{\%}). Hydrolysis of the nitrile group of compound (21), using alkaline hydrogen peroxide, afforded the amide (22) (71{\%}) which was deprotected to give 3(5)-carbamoyl-4-nitro-5(3)-{\ss}-D-ribofuranosylpyrazole (23) (83{\%}). Catalytic reduction of compound (23) gave 4-amino-3(5)-carbamoyl-5(3)-{\ss}-D- ribofuranosylpyrazole (5) (83{\%}) which could be converted into formycin B (24) (69{\%}).",
author = "Buchanan, {J. Grant} and Saxena, {Naveen K.} and Wightman, {Richard H.}",
year = "1984",
language = "English",
pages = "2367--2370",
journal = "Journal of the Chemical Society, Perkin Transactions 1",
issn = "1472-7781",

}

TY - JOUR

T1 - C-nucleoside studies. Part 17. The synthesis of 3(5)-carbamoyl-5(3)-β- D ribofuranosylpyrazole (4-deoxypyrazofurin) and 4-amino-3(5)-carbamoyl-5(3)- β-D-ribofuranosylpyrazole

AU - Buchanan, J. Grant

AU - Saxena, Naveen K.

AU - Wightman, Richard H.

PY - 1984

Y1 - 1984

N2 - 4-Amino-3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-ß-D-ribofuranosyl)pyrazole (10) was converted into the diazopyrazole (11) by treatment with nitrous acid. On photolysis in aqueous dioxane using visible light compound (11) gave 3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-ß-D-ribofuranosyl)pyrazole (12) [48% from (10)] which formed the corresponding amide (13) (75%) with alkaline hydrogen peroxide. Deprotection of compound (13) with methanolic ammonia afforded 3(5)-carbamoyl-5(3)-ß-D-ribofuranosylpyrazole (4) (74%), the 4-deoxy analogue of pyrazofurin (3). 3(5)-Cyano-4-nitro-5(3)-(2,3,5-tri-O- acetyl-ß-D-ribofuranosyl)pyrazole (1) reacted with dihydropyran and toluene-p-sulphonic acid to give the N-tetrahydropyranyl derivative (21) (66.5%). Hydrolysis of the nitrile group of compound (21), using alkaline hydrogen peroxide, afforded the amide (22) (71%) which was deprotected to give 3(5)-carbamoyl-4-nitro-5(3)-ß-D-ribofuranosylpyrazole (23) (83%). Catalytic reduction of compound (23) gave 4-amino-3(5)-carbamoyl-5(3)-ß-D- ribofuranosylpyrazole (5) (83%) which could be converted into formycin B (24) (69%).

AB - 4-Amino-3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-ß-D-ribofuranosyl)pyrazole (10) was converted into the diazopyrazole (11) by treatment with nitrous acid. On photolysis in aqueous dioxane using visible light compound (11) gave 3(5)-cyano-5(3)-(2,3,5-tri-O-acetyl-ß-D-ribofuranosyl)pyrazole (12) [48% from (10)] which formed the corresponding amide (13) (75%) with alkaline hydrogen peroxide. Deprotection of compound (13) with methanolic ammonia afforded 3(5)-carbamoyl-5(3)-ß-D-ribofuranosylpyrazole (4) (74%), the 4-deoxy analogue of pyrazofurin (3). 3(5)-Cyano-4-nitro-5(3)-(2,3,5-tri-O- acetyl-ß-D-ribofuranosyl)pyrazole (1) reacted with dihydropyran and toluene-p-sulphonic acid to give the N-tetrahydropyranyl derivative (21) (66.5%). Hydrolysis of the nitrile group of compound (21), using alkaline hydrogen peroxide, afforded the amide (22) (71%) which was deprotected to give 3(5)-carbamoyl-4-nitro-5(3)-ß-D-ribofuranosylpyrazole (23) (83%). Catalytic reduction of compound (23) gave 4-amino-3(5)-carbamoyl-5(3)-ß-D- ribofuranosylpyrazole (5) (83%) which could be converted into formycin B (24) (69%).

M3 - Article

SP - 2367

EP - 2370

JO - Journal of the Chemical Society, Perkin Transactions 1

JF - Journal of the Chemical Society, Perkin Transactions 1

SN - 1472-7781

ER -