Nucleosides. 130. Synthesis of 2′‐deoxy‐2′‐substituted‐ and 5′‐deoxy‐5′‐substituted‐ψ‐uridine derivatives. Crystalline and molecular structure of 2′‐chloro‐2′‐deoxy‐1,3‐dimethyl‐ψ‐uridine. Studies directed toward the synthesis of 2′‐deoxy‐2′‐substituted‐arabino‐nucleosides. 1 Journal Article
| Authors: | Pankiewicz, K. W.; Watanabe, K. A.; Takayanagi, H.; Itoh, T.; Ogura, H. |
| Article Title: | Nucleosides. 130. Synthesis of 2′‐deoxy‐2′‐substituted‐ and 5′‐deoxy‐5′‐substituted‐ψ‐uridine derivatives. Crystalline and molecular structure of 2′‐chloro‐2′‐deoxy‐1,3‐dimethyl‐ψ‐uridine. Studies directed toward the synthesis of 2′‐deoxy‐2′‐substituted‐arabino‐nucleosides. 1 |
| Abstract: | A method was developed to prepare 5′‐deoxy‐5′‐substituted‐ψ‐uridine derivatives 4 from 3′,5′‐O‐(1, 1, 3, 3‐tetraisopropyldisiloxanyl)‐1,3‐dimethyl‐ψ‐uridine 1 via a silyl rearrangement reaction. Nucleophilic displacement of the mesyloxy function of 2′‐O‐mesyl‐1,3‐dimethyl‐ψ‐uridine 7 afforded products with the 2′‐substituent in the “down” ribo configuration 8. X‐Ray crystallographic analysis of the 2′‐chloro derivative 8a firmly established the molecular structure of 8 and provided evidence for neighboring group participation of the 4‐carbonyl function of 7 during the nucleophilic reactions. Treatment of 1,3‐dimethyl‐ψ‐uridine 11 with α‐acetoxyisobutyryl chloride afforded a mixture from which two 2′‐chloro‐2′‐deoxy‐C‐nucleosides were obtained. The major product (33% yield) was identical with 8. The minor product (7% yield) was consequently assigned the arabino nucleoside 14. This is the first direct introduction of a 2′‐substituent in the “up” configuration in a preformed pyrimidine nucleoside. Copyright © 1985 Journal of Heterocyclic Chemistry |
| Keywords: | nonhuman; drug structure; drug synthesis; nuclear magnetic resonance; theoretical study; drug identification; priority journal; drug analysis; 1,3 dimethylpseudouridine; 2' deoxy 1,3 dimethylpseudouridine; 2' deoxy 1,3 dimethylpseudouridine derivative; 3' deoxy 1,3 dimethylpseudouridine; 5' deoxy 1,3 dimethylpseudouridine; 5' deoxy 1,3 dimethylpseudouridine derivative |
| Journal Title: | Journal of Heterocyclic Chemistry |
| Volume: | 22 |
| Issue: | 6 |
| ISSN: | 0022-152X |
| Publisher: | Wiley-Blackwell Publishing, Inc. |
| Date Published: | 1985-11-01 |
| Start Page: | 1703 |
| End Page: | 1710 |
| Language: | English |
| DOI: | 10.1002/jhet.5570220646 |
| PROVIDER: | scopus |
| DOI/URL: | |
| Notes: | Article -- Export Date: 26 October 2021 -- Source: Scopus |
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