Treatment of 2,,3'-0-methoxyethylideneadenosine (1) with excess pivalic acid chloride in refluxing pyridine gave a mixture composed primarily of 6-lV-pivalamido-9-(3-chloro-3-deoxy-2-0-acetyI-5-0-pivalyl-d-D-xylofuranosyljpurine (2a) and 6-lV-pivalamido-9-(3-chloro-3-deoxy-5-0-pivalyl-2-0-[4,4-dimethyl-3-pivalyloxypent-2enoy 1]-ß-d-xylofuranosyl)purine (2b) in high combined yield. Methanolic sodium methoxide converted this mixture to 9-(2,3-anhydro-/3-D-ribofuranosyl)adenine (adenosine ribo-epoxide) (3) in greater than 60% overall yield from starting adenosine. The epoxide 3 was found to spontaneously decompose (presumably via the N3-*^'xylo-cyclonucleoside, i) to the ring-opened aminoimidazole carboxamidine cyclonucleoside ii in water. Sodium hydroxide smoothly effected transformation of ii to the corresponding carboxamide, iii. Pivalylation and benzoylation of 3 in pyridine with the appropriate acid chloride gave 6-M-pivalamido-9-(5-0-pivalyl-2,3-anhydroß-o -ribofuranosyl)purine ( 4) and the corresponding N,N, 08,-tribenzoate, 6, respectively. Tetraethylammonium fluoride in refluxing acetonitrile followed by methoxide deblocking converted 4 or 6 into 9-(3-fluoro-3-deoxy-/3-D-xylofuranosyl)adenine ( 7). Reaction of 6 with sodium benzoate in moist DMF followed by deblocking gave 9-/3-d -xylofuranosyladenine (adenine xyloside) (8) in high yield. Treatment of 6 with sodium azide in hot DMF gave 9-(3-azido-3-deoxy-/3-n-xylofuranosyl)adenine (9a) in excellent yield after removal of protecting groups. Hydrogenation of 9a gave 9-(3-amino-3-deoxy-/3 -d -xylofuranosyl) adenine (9b). Treatment of the crude product [presumably a mixture of N-benzoylated 9-(3,5-di-0-benzoyl-/3-D-xylofuranosyl)adenines] from sodium benzoate
Reaction of tubercidin (4-amino-7-~-~-ribofuranosylpyrrolo[2,3-d]pyrimidine)(1) with a-acetoxyisobutyryl chloride in the presence of excess sodium iodide in acetonitrile gave an acylated iodo intermediate (2) which was converted into 3'-deoxytubercidin (4) by hydrogenolysis and subsequent saponification.Analogous treatment of formycin (7-amino-3-~-~-ribofuranosylpyrazo10[4,3-d]pyrimidine) (5) gave 3'-deoxyformycin (6) and 2'-deoxyformycin (7) in an approximate ratio of 3:2. These purified nucleosides, 6 and 7 were individually deaminated enzymatically to give 3'-deoxyformycin B (8) and 2'-deoxyformycin B (9).Biological rationale, n.m.r., and mass spectra of these antibiotic-derived deoxynucleosides are discussed.La rCaction de la tubercidine (amino-4 p-D-ribofuranosyl-7 pyrrolo pyrimidine [2,3-dl) (1) avec le chlorure d'a-acetoxyisobutyryle en presence d'un exces d'iodure de sodium dans I'acttonitrile donne un intermediaire iodo acylC (2) qui a etC transforme en deoxy-3' tubercidine (4) par hydroginolyse suivie d'une saponification.Le traitenlent identique de la formycine (amino-7 a-D-ribofuranosyl-3 pyrazolo pyrimidine [4,3-dl) (5) donne la dioxy-3' formycine (6) et la dioxy-2' formicyne (7) dans un rapport approximativement Cgal a 3:2. Les nucleosides purifies, 6 et 7, donnent respectivement la deoxy-3'formycine B(8) et la dkoxy-2' formycine B(9) lorsque I'on enleve leur groupement amine par action enzymatique.Les caracteristiques biologiques ainsi que les spectres de masse et r.m.n. de ces dCoxynuclCosides derives d'antibiotiques sont discutts.[Traduit par le journal]Can. J. Chern., 5 1 . 1313 (1973) We wish to report the synthesis of 3'-deoxyThe nucleoside antibiotics tubercidin (1) and tubercidin (4), 3'-deoxyformycin (6), and 2'-formycin (5) have been studied in considerable deoxyformycin (7) using the "abnormal" reaction detail in biological systems and a comprehensive of a-acetoxyisobutyryl halides with diols dis-review is available (3). Formycin (5) is currently covered by Mattocks (1) and first applied to undergoing investigation in molecular biology nucleosides by Moffatt and coworkers (2).
D i e Synthese von vorwiegcnd N-8-phenylsubstituierten Pterinen wird besLhrieben. Die komplexen Strukturverhaltnwe der verschledenen Molekultormcn in Abhangigkelt vom pH-Wert werden anhand von UVund NMR-Spektren 5ouie pK-Werten besprochen Durch die lsolierung des 3.6-Dimethyl-8-phenyl-7-methylen-7 8-dihydro-pterins (62) konnte sichergestellt werdeii, da8 8-aubstituierte 6 7-[>imethyl-pteridin-Derivate im dlkalischen Bereich nicht unter Ringoffnung sondern unter Deprotonierung an 7-CH3 reagieren.
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