Nucleosides. 121. Improved and General Synthesis of 2′-Deoxy C-Nucleosides. Synthesis of 5-(2-Deoxy-β-D-erythro-pentofuranosyl)uracil, -1-methyluracil, -1,3-dimethyluracil, and -isocytosine

Krzysztof Pankiewicz, Akira Matsuda, Kyoichi A. Watanabe

Research output: Contribution to journalArticle

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Abstract

5-(2-Deoxy-²-D-erythro-pentoniranosyl)-l,3-dimethyluracil (6a), -1-methyluracil (6b), -uracil (6c), and -isocytosine (6d) were synthesized. Compounds 6b−d are C-nucleoside isosteres of thymidine, 2′-deoxyuridine, and 2′-deoxycytidine, respectively. 1,3-Dimethylpseudouridine (la), 1-methylpseudouridine (lb), pseudouridine (lc), and pseudoisocytidine (1d) were treated with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane in pyridine to afford the corresponding 3′,5′-tetraisopropyldisiloxanyl derivatives 2 which were converted into the respective 2′-O-[(imidazol-1-yl)thiocarbonyl] C-nucleosides 3. Compounds 3a,b were converted directly into the corresponding 2′-deoxy β-C-nucleosides 5a,b exclusively by reduction with n-Bu3SnH. For the synthesis of 2′-deoxy β-C-nucleosides 5c,d, the intermediates 3c,d were trimethylsilylated prior to n-Bu3SnH treatment. Deprotection of 5a−d was effected by treatment with n-Bu4NF, and the corresponding free 2′-deoxy β-C-nucleosides 6a−d were obtained in good yields.

Original languageEnglish (US)
Pages (from-to)485-488
Number of pages4
JournalJournal of Organic Chemistry
Volume47
Issue number3
DOIs
StatePublished - Jan 1 1982

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Uracil
Nucleosides
Pseudouridine
Deoxyuridine
Deoxycytidine
Thymidine
1,3-dimethyluracil
1-methyluracil
isocytosine
Derivatives

Cite this

Nucleosides. 121. Improved and General Synthesis of 2′-Deoxy C-Nucleosides. Synthesis of 5-(2-Deoxy-β-D-erythro-pentofuranosyl)uracil, -1-methyluracil, -1,3-dimethyluracil, and -isocytosine. / Pankiewicz, Krzysztof; Matsuda, Akira; Watanabe, Kyoichi A.

In: Journal of Organic Chemistry, Vol. 47, No. 3, 01.01.1982, p. 485-488.

Research output: Contribution to journalArticle

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abstract = "5-(2-Deoxy-²-D-erythro-pentoniranosyl)-l,3-dimethyluracil (6a), -1-methyluracil (6b), -uracil (6c), and -isocytosine (6d) were synthesized. Compounds 6b−d are C-nucleoside isosteres of thymidine, 2′-deoxyuridine, and 2′-deoxycytidine, respectively. 1,3-Dimethylpseudouridine (la), 1-methylpseudouridine (lb), pseudouridine (lc), and pseudoisocytidine (1d) were treated with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane in pyridine to afford the corresponding 3′,5′-tetraisopropyldisiloxanyl derivatives 2 which were converted into the respective 2′-O-[(imidazol-1-yl)thiocarbonyl] C-nucleosides 3. Compounds 3a,b were converted directly into the corresponding 2′-deoxy β-C-nucleosides 5a,b exclusively by reduction with n-Bu3SnH. For the synthesis of 2′-deoxy β-C-nucleosides 5c,d, the intermediates 3c,d were trimethylsilylated prior to n-Bu3SnH treatment. Deprotection of 5a−d was effected by treatment with n-Bu4NF, and the corresponding free 2′-deoxy β-C-nucleosides 6a−d were obtained in good yields.",
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N2 - 5-(2-Deoxy-²-D-erythro-pentoniranosyl)-l,3-dimethyluracil (6a), -1-methyluracil (6b), -uracil (6c), and -isocytosine (6d) were synthesized. Compounds 6b−d are C-nucleoside isosteres of thymidine, 2′-deoxyuridine, and 2′-deoxycytidine, respectively. 1,3-Dimethylpseudouridine (la), 1-methylpseudouridine (lb), pseudouridine (lc), and pseudoisocytidine (1d) were treated with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane in pyridine to afford the corresponding 3′,5′-tetraisopropyldisiloxanyl derivatives 2 which were converted into the respective 2′-O-[(imidazol-1-yl)thiocarbonyl] C-nucleosides 3. Compounds 3a,b were converted directly into the corresponding 2′-deoxy β-C-nucleosides 5a,b exclusively by reduction with n-Bu3SnH. For the synthesis of 2′-deoxy β-C-nucleosides 5c,d, the intermediates 3c,d were trimethylsilylated prior to n-Bu3SnH treatment. Deprotection of 5a−d was effected by treatment with n-Bu4NF, and the corresponding free 2′-deoxy β-C-nucleosides 6a−d were obtained in good yields.

AB - 5-(2-Deoxy-²-D-erythro-pentoniranosyl)-l,3-dimethyluracil (6a), -1-methyluracil (6b), -uracil (6c), and -isocytosine (6d) were synthesized. Compounds 6b−d are C-nucleoside isosteres of thymidine, 2′-deoxyuridine, and 2′-deoxycytidine, respectively. 1,3-Dimethylpseudouridine (la), 1-methylpseudouridine (lb), pseudouridine (lc), and pseudoisocytidine (1d) were treated with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane in pyridine to afford the corresponding 3′,5′-tetraisopropyldisiloxanyl derivatives 2 which were converted into the respective 2′-O-[(imidazol-1-yl)thiocarbonyl] C-nucleosides 3. Compounds 3a,b were converted directly into the corresponding 2′-deoxy β-C-nucleosides 5a,b exclusively by reduction with n-Bu3SnH. For the synthesis of 2′-deoxy β-C-nucleosides 5c,d, the intermediates 3c,d were trimethylsilylated prior to n-Bu3SnH treatment. Deprotection of 5a−d was effected by treatment with n-Bu4NF, and the corresponding free 2′-deoxy β-C-nucleosides 6a−d were obtained in good yields.

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