The Synthesis of 2′-Deoxyadenosine <i>via</i> Stereospecific Coupling Reaction

Kawakami, Hiroshi; Matsushita, Hajime; Naoi, Y.; Itoh, Kazuo; Yoshikoshi, H.

doi:10.1246/cl.1989.235

Cited by 23 publications

(6 citation statements)

References 7 publications

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“…Na(adeninate), [AuCl(PMe 3 )], [AuCl(PTA)], and Tl(acac) were prepared according to previously reported methods. Adenine (6-aminopurine, Sigma-Aldrich) was used as received.…”

Section: Experimental Sectionsupporting

confidence: 78%

Cooperative Au(I)···Au(I) Interactions and Hydrogen Bonding as Origin of a Luminescent Adeninate Hydrogel Formed by Ultrathin Molecular Nanowires

et al. 2018

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Two water-soluble [Au( N-adeninate)(PR)] complexes (PR = PMe (1); PTA (3)) were synthesized by the coordination of the respective cationic [Au(PR)] fragment to the N position of the adeninate anion. Both complexes crystallize as dimers by aurophilic contacts of 3.2081(6) Å in 1 and 3.0942(7) and 3.0969(7) Å in 3, but different packings are observed due to the crystallizing solvent choice and the nature of the ancillary phosphine ligand. At this regard, different supramolecular behavior is observed in water, ranges from the formation of ultrathin nanowires of 5.3 ± 1.9 nm of diameter and up to 1.5 μm in length and leads to a blue-luminescent hydrogel for 1, to the single-crystallization of 3. Parallel computational studies carried out show that aurophilicity and N-H···N or O-H···N hydrogen bonding are comparable in strength, suggesting a competition between all types of weak forces in the final observed macroscopic properties.

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“…Na(adeninate), [AuCl(PMe 3 )], [AuCl(PTA)], and Tl(acac) were prepared according to previously reported methods. Adenine (6-aminopurine, Sigma-Aldrich) was used as received.…”

Section: Experimental Sectionsupporting

confidence: 78%

Cooperative Au(I)···Au(I) Interactions and Hydrogen Bonding as Origin of a Luminescent Adeninate Hydrogel Formed by Ultrathin Molecular Nanowires

et al. 2018

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“…Miniscule purinesalt concentrations severely limit the rates of S N 2 glycosylation in two-phase solution/salt mixtures; anomerization of the chlorosugar becomes increasingly problematic with time. Purine salts have slightly increased solubility in the more polar acetone, but yields were low to moderate; 19,24 stereoselective glycosylations of 7-deazapurines with 5-deoxy-2,3-O-isopropylidene-R-D-ribofuranosyl chloride in toluene were effected with phase transfer catalysis. 25 We first mixed a purine sodium salt in DMF or acetonitrile (ACN) with a solution of 2-deoxy-3,5-di-O-(p-toluoyl)-R-Derythro-pentofuranosyl chloride in DMF or ACN.…”

Section: Resultsmentioning

confidence: 99%

Regiospecific and Highly Stereoselective Coupling of 6-(Substituted-imidazol-1-yl)purines with 2-Deoxy-3,5-di-O-(p-toluoyl)-α-d-erythro-pentofuranosyl Chloride. Sodium-Salt Glycosylation in Binary Solvent Mixtures: Improved Synthesis of Cladribine¹

2006

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Glycosylation of 6-(substituted-imidazol-1-yl)purine sodium salts with 2-deoxy-3,5-di-O-(p-toluoyl)-alpha-D-erythro-pentofuranosyl chloride proceeds with regiospecific formation of the N9 isomers. Base substrates with lipophilic substituents on the C6-linked imidazole moiety are more soluble in organic solvents, and the solubility is further increased with binary solvent mixtures. Selective solvation also diminishes the extent of anomerization of the chlorosugar. Stirred reaction mixtures of the modified-purine sodium salts generated in a polar solvent and cooled solutions of the protected 2-deoxysugar chloride in a nonpolar solvent give 2'-deoxynucleoside derivatives with N9 regiochemistry and enhanced beta/alpha configuration ratios. Application of the binary-solvent methodology with 2-chloro-6-(substituted-imidazol-1-yl)purine salts in cold acetonitrile and the chlorosugar in cold dichloromethane gives essentially quantitative yields of the N9 isomers of beta-anomeric 2'-deoxynucleoside intermediates. Direct ammonolysis (NH(3)/MeOH) of such intermediates or benzylation of the imidazole ring followed by milder ammonolysis of the imidazolium salt gives high yields of the clinical anticancer drug cladribine (2-chloro-2'-deoxyadenosine).

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“…The above-mentioned nucleosides can be prepared by chemical synthesis, generally by a glycosylation reaction; however, this approach requires time-consuming multistage processes plagued by low yields and the formation of undesired byproducts. Particularly, the synthesis of purine 2‘-deoxynucleosides still remains a practical challenge using strategies reported in the literature, since the reaction of purine base and activated 2‘-deoxyribose produces both anomeric isomers and regioisomers . Alternatively, 2‘-deoxynucleosides can be prepared via an enzymatic process, that is, by a transglycosylation reaction between a nucleoside and a purine or pyrimidine base in aqueous solution catalyzed by nucleoside phosphorylases or microorganisms that produce them …”

Section: Introductionmentioning

confidence: 99%

Immobilization and Stabilization of Recombinant Multimeric Uridine and Purine Nucleoside Phosphorylases fromBacillus subtilis

et al. 2004

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We selected the PnpI/PupG (PNP) with specificity for ribo- and deoxyriboguanosine and ribo- and deoxyriboinosine and the Up/Pdp (UP) with specificity for uridine, thymidine, and deoxyuridine from the purine and pyrimidine salvage pathway of the Gram-positive bacterium Bacillus subtilis. Then, an extensive study of the UP (uridine phosphorylase) and PNP (purine nucleoside phosphorylase) immobilization and stabilization was carried out: optimal UP preparation was achieved by immobilization onto Sepabeads coated with poly(ethyleneimine) and finally cross-linked with aldehyde dextran (UP-Sep-PEI-Dx); optimal immobilized PNP was prepared onto glyoxyl-agarose. Both derivatives were highly stable and active even under drastic experimental conditions (pH 10, 45 degrees C) unlike the free enzymes which were promptly inactivated. The derivatives prepared were successfully used in the synthesis of 2'-deoxyguanosine by enzymatic transglycosylation in aqueous solution between 2'-deoxyuridine and guanine.

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The Synthesis of 2′-Deoxyadenosine via Stereospecific Coupling Reaction

Cited by 23 publications

References 7 publications

Cooperative Au(I)···Au(I) Interactions and Hydrogen Bonding as Origin of a Luminescent Adeninate Hydrogel Formed by Ultrathin Molecular Nanowires

Cooperative Au(I)···Au(I) Interactions and Hydrogen Bonding as Origin of a Luminescent Adeninate Hydrogel Formed by Ultrathin Molecular Nanowires

Regiospecific and Highly Stereoselective Coupling of 6-(Substituted-imidazol-1-yl)purines with 2-Deoxy-3,5-di-O-(p-toluoyl)-α-d-erythro-pentofuranosyl Chloride. Sodium-Salt Glycosylation in Binary Solvent Mixtures: Improved Synthesis of Cladribine¹

Immobilization and Stabilization of Recombinant Multimeric Uridine and Purine Nucleoside Phosphorylases fromBacillus subtilis

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The Synthesis of 2′-Deoxyadenosine via Stereospecific Coupling Reaction

Cited by 23 publications

References 7 publications

Cooperative Au(I)···Au(I) Interactions and Hydrogen Bonding as Origin of a Luminescent Adeninate Hydrogel Formed by Ultrathin Molecular Nanowires

Cooperative Au(I)···Au(I) Interactions and Hydrogen Bonding as Origin of a Luminescent Adeninate Hydrogel Formed by Ultrathin Molecular Nanowires

Regiospecific and Highly Stereoselective Coupling of 6-(Substituted-imidazol-1-yl)purines with 2-Deoxy-3,5-di-O-(p-toluoyl)-α-d-erythro-pentofuranosyl Chloride. Sodium-Salt Glycosylation in Binary Solvent Mixtures: Improved Synthesis of Cladribine1

Immobilization and Stabilization of Recombinant Multimeric Uridine and Purine Nucleoside Phosphorylases fromBacillus subtilis

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Product

Resources

About

Regiospecific and Highly Stereoselective Coupling of 6-(Substituted-imidazol-1-yl)purines with 2-Deoxy-3,5-di-O-(p-toluoyl)-α-d-erythro-pentofuranosyl Chloride. Sodium-Salt Glycosylation in Binary Solvent Mixtures: Improved Synthesis of Cladribine¹