Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin Synthesis
During the preparative synthesis of 2-fluorocordycepin from 2-fluoroadenosine and 3′-deoxyinosine catalyzed by <i>E. coli</i> purine nucleoside phosphorylase, a slowdown of the reaction and decrease of yield down to 5% were encountered. An unknown nucleoside was found in the reaction mix...
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2021-04-01
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| Series: | Biomolecules |
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| Online Access: | https://www.mdpi.com/2218-273X/11/4/539 |
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| author | Alexey L. Kayushin Julia A. Tokunova Ilja V. Fateev Alexandra O. Arnautova Maria Ya. Berzina Alexander S. Paramonov Olga I. Lutonina Elena V. Dorofeeva Konstantin V. Antonov Roman S. Esipov Igor A. Mikhailopulo Anatoly I. Miroshnikov Irina D. Konstantinova |
| author_facet | Alexey L. Kayushin Julia A. Tokunova Ilja V. Fateev Alexandra O. Arnautova Maria Ya. Berzina Alexander S. Paramonov Olga I. Lutonina Elena V. Dorofeeva Konstantin V. Antonov Roman S. Esipov Igor A. Mikhailopulo Anatoly I. Miroshnikov Irina D. Konstantinova |
| author_sort | Alexey L. Kayushin |
| collection | DOAJ |
| description | During the preparative synthesis of 2-fluorocordycepin from 2-fluoroadenosine and 3′-deoxyinosine catalyzed by <i>E. coli</i> purine nucleoside phosphorylase, a slowdown of the reaction and decrease of yield down to 5% were encountered. An unknown nucleoside was found in the reaction mixture and its structure was established. This nucleoside is formed from the admixture of 2′,3′-anhydroinosine, a byproduct in the preparation of 3-′deoxyinosine. Moreover, 2′,3′-anhydroinosine forms during radical dehalogenation of 9-(2′,5′-di-<i>O</i>-acetyl-3′-bromo- -3′-deoxyxylofuranosyl)hypoxanthine, a precursor of 3′-deoxyinosine in chemical synthesis. The products of 2′,3′-anhydroinosine hydrolysis inhibit the formation of 1-phospho-3-deoxyribose during the synthesis of 2-fluorocordycepin. The progress of 2′,3′-anhydroinosine hydrolysis was investigated. The reactions were performed in D<sub>2</sub>O instead of H<sub>2</sub>O; this allowed accumulating intermediate substances in sufficient quantities. Two intermediates were isolated and their structures were confirmed by mass and NMR spectroscopy. A mechanism of 2′,3′-anhydroinosine hydrolysis in D<sub>2</sub>O is fully determined for the first time. |
| first_indexed | 2024-03-10T12:32:57Z |
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| id | doaj.art-87d96404467d4b1785d17ba5e85c74d5 |
| institution | Directory Open Access Journal |
| issn | 2218-273X |
| language | English |
| last_indexed | 2024-03-10T12:32:57Z |
| publishDate | 2021-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Biomolecules |
| spelling | doaj.art-87d96404467d4b1785d17ba5e85c74d52023-11-21T14:29:59ZengMDPI AGBiomolecules2218-273X2021-04-0111453910.3390/biom11040539Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin SynthesisAlexey L. Kayushin0Julia A. Tokunova1Ilja V. Fateev2Alexandra O. Arnautova3Maria Ya. Berzina4Alexander S. Paramonov5Olga I. Lutonina6Elena V. Dorofeeva7Konstantin V. Antonov8Roman S. Esipov9Igor A. Mikhailopulo10Anatoly I. Miroshnikov11Irina D. Konstantinova12Shemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaInstitute of Bioorganic Chemistry, National Academy of Sciences, Acad. Kuprevicha 5/2, 220141 Minsk, BelarusShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaShemyakin and Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya 16/10, 117997 GSP, B-437 Moscow, RussiaDuring the preparative synthesis of 2-fluorocordycepin from 2-fluoroadenosine and 3′-deoxyinosine catalyzed by <i>E. coli</i> purine nucleoside phosphorylase, a slowdown of the reaction and decrease of yield down to 5% were encountered. An unknown nucleoside was found in the reaction mixture and its structure was established. This nucleoside is formed from the admixture of 2′,3′-anhydroinosine, a byproduct in the preparation of 3-′deoxyinosine. Moreover, 2′,3′-anhydroinosine forms during radical dehalogenation of 9-(2′,5′-di-<i>O</i>-acetyl-3′-bromo- -3′-deoxyxylofuranosyl)hypoxanthine, a precursor of 3′-deoxyinosine in chemical synthesis. The products of 2′,3′-anhydroinosine hydrolysis inhibit the formation of 1-phospho-3-deoxyribose during the synthesis of 2-fluorocordycepin. The progress of 2′,3′-anhydroinosine hydrolysis was investigated. The reactions were performed in D<sub>2</sub>O instead of H<sub>2</sub>O; this allowed accumulating intermediate substances in sufficient quantities. Two intermediates were isolated and their structures were confirmed by mass and NMR spectroscopy. A mechanism of 2′,3′-anhydroinosine hydrolysis in D<sub>2</sub>O is fully determined for the first time.https://www.mdpi.com/2218-273X/11/4/539purine nucleoside phosphorylasebiocatalyze3′-deoxyinosine2-fluorocordycepindeuterium oxide |
| spellingShingle | Alexey L. Kayushin Julia A. Tokunova Ilja V. Fateev Alexandra O. Arnautova Maria Ya. Berzina Alexander S. Paramonov Olga I. Lutonina Elena V. Dorofeeva Konstantin V. Antonov Roman S. Esipov Igor A. Mikhailopulo Anatoly I. Miroshnikov Irina D. Konstantinova Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin Synthesis Biomolecules purine nucleoside phosphorylase biocatalyze 3′-deoxyinosine 2-fluorocordycepin deuterium oxide |
| title | Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin Synthesis |
| title_full | Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin Synthesis |
| title_fullStr | Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin Synthesis |
| title_full_unstemmed | Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin Synthesis |
| title_short | Radical Dehalogenation and Purine Nucleoside Phosphorylase <i>E. coli</i>: How Does an Admixture of 2′,3′-Anhydroinosine Hinder 2-fluoro-cordycepin Synthesis |
| title_sort | radical dehalogenation and purine nucleoside phosphorylase i e coli i how does an admixture of 2 3 anhydroinosine hinder 2 fluoro cordycepin synthesis |
| topic | purine nucleoside phosphorylase biocatalyze 3′-deoxyinosine 2-fluorocordycepin deuterium oxide |
| url | https://www.mdpi.com/2218-273X/11/4/539 |
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