Nucleic acid related compounds. 66. Improved syntheses of 5′-chloro-5′-deoxy- and 5′-S-aryl(or alkyl)-5′-thionucleosides

Abstract

Treatment of ribonucleosides with thionyl chloride/pyridine/acetonitrile (0 °C to ambient temperature) resulted in essentially quantitative formation of 5′-chloro-5′-deoxy-2′,3′-O-sulfinylnucleoside derivatives. These diastereomeric sulfite esters underwent deprotection readily with aqueous methanolic ammonia. This gave 5′-chloro-5′-deoxynucleosides without use of the suspected carcinogen, hexamethylphosphoramide (HMPA). Nucleophilic displacement with sodium thiolates in dimethylformamide (−30 °C to ambient temperature) gave 5′-S-aryl(or alkyl)-5′-thionucleosides in high yields. Treatment of ribonucleosides with thionyl chloride/acetonitrile without pyridine followed by aqueous work-up gave diastereomeric 2′,3′-O-sulfinylnucleosides with an unmodified 5′-hydroxyl group. Diagnostic NMR shifts for cyclic sulfite ester stereochemistry are noted. Key words: adenosine, 5′-S-aryl(or alkyl)-5′-thionucleosides, 5′-chloro-5′-deoxynucleosides, uridine, nucleosides.

Adenylate Deaminase (5′‐Adenylic Acid Deaminase, AMPDA)‐Catalyzed Deamination of 5′‐Deoxy‐5′‐Substituted and 5′‐Protected Adenosines: A Comparison with the Catalytic Activity of Adenosine Deaminase (ADA)

“…[7] Treatment of the above intermediate 7 with sodium azide in dimethyl formamide at 80°C directly afforded the deprotected azide 5a (45 %). Compounds 5bϪd were prepared according to Robins and co-workers.…”

Uridine Binding Motifs of Human Concentrative Nucleoside Transporters 1 and 3 Produced inSaccharomyces cerevisiae

“…Chemical, Inc. (Orange, CA). 1-(␤-D-Arabinofuranosyl)uracil (Codington et al, 1960;Hampton and Nichol, 1966), 2Ј-azido-2Ј-deoxyuridine (Verheyden et al, 1971), 2Ј-O-methyluridine (Robins et al, 1974), 1-(␤-D-xylofuranosyl)uracil (Yung and Fox, 1961), 3Ј-deoxyuridine (Rhie and Pfleiderer, 1994), 3Ј-azido-3Ј-deoxyuridine (Matray and Gryaznov, 1999), 5Ј-deoxyuridine (Wang et al, 1977), 5Ј-chloro-5Ј-deoxyuridine (Robins et al, 1991), 5Ј-azido-5Ј-deoxyuridine (Horwitz et al, 1962), and 5Ј-O-methyluridine (Hovinen, 1997) were prepared as described in the references noted. 3Ј,5Ј-Dideoxyuri- The transport of 1 M ͓ 3 H͔Urd into yeast (fui1::TRP) expressing either pYPhCNT1 or pYPhCNT3 was measured over 30 or 10 min, respectively, in the presence of graded concentrations of Urd or Urd analogs.…”

A new 16-membered tetraene macrolide JBIR-100 from a newly identified Streptomyces species

“…piericidin-A (182 (193) were isolated. The polar sub-fraction FIE gave glucopiericidin C (185), 2'-deoxyuridin) [285] and 2'-deoxy-thymidin [286,287] after a series of chromatographic purification steps ( Figure 97). From fraction II, indole-3-carboxylic acid and uracil were isolated.…”