Synthesis of Tubercidin, 6-Chlorotubercidin and Related Nucleosides

Anderson, J. D.; Bontems, Roger J.; Geary, Stewart; Cottam, Howard B.; Larson, Steven B.; Matsumoto, Steven S.; Smee, Donald F.; Robins, Roland K.

doi:10.1080/07328318908054327

Cited by 16 publications

(16 citation statements)

References 28 publications

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“…From Table 3, it is obvious that a change of the glycosylation position causes changes in the UV-spectra. When the UV-spectra of the N-1 nucleosides 14 and 16 are compared to their N-7 counterparts 12 and 1b (toyocamycin), an additional maximum around 312 nm appears, a finding which was already reported for other pyrrolo [2,3-d]pyrimidines with a functionalized pyrrole moiety (compounds 27, 28 [48] ).…”

Section: Methodsmentioning

confidence: 72%

“…According to observations made on other isomeric pyrrolo[2,3-d]pyrimidine nucleosides, N-7 was established as glycosylation site for the sugar residues linked to the pyrrole moiety and N-1 for the isomers with the sugar attached to the pyrimidine system. [43,48] In both series of isomers, the removal of the bromine substituent (15, 17) induces a downfield shift for the C-6 (ca. 10 ppm) and an upfield shift of C-5 (Table 1).…”

Section: Methodsmentioning

confidence: 99%

“…[55] Also, nucleobase anion glycosylation was successful for the synthesis of 6-halogenated derivatives reported by Kazimierczuk [41] and Anderson. [48] CONCLUSION The 4-amino-7H -pyrrolo[2,3-d]pyrimidines such as 9 form the N-7 isomer 11 as main product with the N-1 derivatives as minor component (13), when "one-pot" glycosylation conditions (MeCN, silylated base, TMSOTf) are employed. The corresponding 4-hydroxy-7H -pyrrolo[2,3-d]pyrimidine (21) or 2-hydroxy-7H -pyrrolo[2,3-d]pyrimidine (24) give the N-3 isomers almost exclusively.…”

Section: Downloaded By [Gazi University] At 02:13 06 February 2015mentioning

confidence: 99%

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Studies on the Glycosylation of Pyrrolo[2,3-d] Pyrimidines with 1-O-Acetyl-2,3,5-Tri-O-Benzoyl-β-D-Ribofuranose: The Formation of Regioisomers During Toyocamycin and 7-Deazainosine Syntheses

Leonard

Ingale

Ding

et al. 2009

Nucleosides, Nucleotides & Nucleic Acids

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Glycosylation of silylated 4-amino-6-bromo-5-cyano-7H-pyrrolo[2,3-d]pyrimidine (9) with 1-O-acetyl-2,3,5-tri-O-benzoyl-beta-D-ribofuranose (10) under "one-pot" glycosylation conditions (MeCN, TMSOTf) yielded the N-7 isomer 11 together with the N-1 compound 13 (ratio = 2:1). When the same conditions were applied to 4-hydroxy-7H-pyrrolo[2,3-d]pyrimidine (21) the N-3 isomer 22 was the only glycosylation product formed in almost quantitative yield.

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Section: Methodsmentioning

confidence: 72%

Section: Methodsmentioning

confidence: 99%

Section: Downloaded By [Gazi University] At 02:13 06 February 2015mentioning

confidence: 99%

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Studies on the Glycosylation of Pyrrolo[2,3-d] Pyrimidines with 1-O-Acetyl-2,3,5-Tri-O-Benzoyl-β-D-Ribofuranose: The Formation of Regioisomers During Toyocamycin and 7-Deazainosine Syntheses

Leonard

Ingale

Ding

et al. 2009

Nucleosides, Nucleotides & Nucleic Acids

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“…A 74% yield of the desired 2,5,7-trichlorothiazolo[4,5-d]pyrimidine (20) was obtained along with a small amount of 5,7-dichloro- (21). The structure of 21 was assigned unequivocally by single-crystal X-ray analysis and is detailed e 1 s e~h e r e .…”

Section: Chemistrymentioning

confidence: 99%

“…After evaporation of the solvent, the residue was dissolved in EtOAc (250 mL), washed with water (2 x 50 mL), dried over sodium sulfate, and evaporated. The resulting foam was purified by silica gel column chromatography using CHCI3-acetone 7:l. The product was crystallized from EtOH to give a white powder: yield, 2.0 g, 67%; mp 112-114 "C; IR showed no azide band in the region of 2100-2200 cm-'; UV A , (pH 1) 232 nm (c 39800), 270 (13500) (20). A mixture of 2-chlorothiazolo[4,5-d]pyrimidine-5,7(4H,61F)-dione13 (19; 15.8 g, 78 mmol), POCl, (220 mL), and N,N-dimethylaniline (12.3 g, 0.1 mol) was refluxed for 3 h. The excess POCl, was removed under reduced pressure and the residue was poured into ice-water (500 mL) with stirring.…”

mentioning

confidence: 99%

Thiazolo[4,5-d]pyrimidine nucleosides. The synthesis of certain 3-.beta.-D-ribofuranosylthiazolo[4,5-d]pyrimidines as potential immunotherapeutic agents

Nagahara¹,

Anderson²,

Kini³

et al. 1990

J. Med. Chem.

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Novel analogues of the naturally occurring purine nucleosides were synthesized in the thiazolo[4,5-d]pyrimidine ring system to determine the immunomodulatory effects of insertion of a sulfur atom in place of nitrogen at position 7 of the purine ring. In particular, 5-amino-3-beta-D-ribofuranosylthiazolo[4,5-d]pyrimidine-2,7(3H,6H) -dione (7, guanosine analogue), 3-beta-D-ribofuranosylthiazolo[4,5-d]pyrimidine-2,5,7(3H,4H,6H) trione (8, xanthosine analogue), 3-beta-D-ribofuranosylthiazolo[4,5-d]pyrimidine-2,7(3H,6H)-dione (10, inosine analogue), and 7-amino-3-beta-D-ribofuranosylthiazolo[4,5-d]pyrimidin-2(3H)-one (32, adenosine analogue) were prepared, as well as the 8-mercaptoguanosine (14) and 6-mercaptoguanosine (17) analogues. Single-crystal X-ray studies confirmed the structural assignment of 17 and 32 as having the beta-configuration with the site of glycosylation at N3. The nucleosides were evaluated for their ability to potentiate various murine immune functions in direct comparison to the known active agents 8-bromoguanosine (1), 8-mercaptoguanosine (2), and 7-methyl-8-oxoguanosine (3). Two of the guanosine analogues, 7 and 14, were found to exhibit significant immunoactivity relative to the positive control compounds (1-3), while the adenosine, inosine, xanthosine, and 6-mercaptoguanosine analogues were devoid of activity. Compound 7 exhibited greater immunoactivity than any of the other guanosine analogues and derivatives in all test systems. Specifically, 7 was shown to be about twice as potent as 3 in the murine spleen cell mitogenicity assay. In addition, treatment with 7 produced about a 4-fold increase in natural killer cell cytotoxicity, while treatment with 3 afforded a 3-fold increase over controls. Finally, 7 provided excellent protection (92% survivors compared to 0% for placebo controls) against Semliki Forest virus in mice. Induction of interferon may account for the major mode of action of these guanosine analogues.

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9‐Deazapurine nucleosides. The synthesis of certain N‐5‐β‐d‐ribofuranosylpyrrolo[3,2‐d]pyrimidines

Girgis¹,

Robins²,

Cottam³

1990

Journal of Heterocyclic Chem

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Several N‐5 ribofuranosyl‐2,4‐disubstituted pyrrolo[3,2‐d]pyrimidine (9‐deazapurine) nucleosides were prepared by the single phase sodium salt glycosylation of 2,4‐dichloro‐5H‐pyrrolo[3,2‐d]pyrimidine (3) using 1‐chloro‐2,3‐O‐isopropylidene‐5‐O‐(t‐butyl)dirnethylsilyl‐α‐D‐ribofuranose (2). Use of 2 for the glycosylation avoided the formation of “orthoamide” products 1 and provided an excellent yield of the β nucleoside, 2,4‐dichloro‐5‐[2,3‐O‐isopropylidene‐5‐O‐(t‐butyl)dimethylsilyl‐β‐D‐ribofuranosyl]‐5H‐pyrrolo[3,2‐d]pyrimidine (4), along with a small amount of the corresponding α anomer, 5. Compound 4 served as the versatile intermediate from which the N‐7 ribofuranosyl analogs of the naturally‐occurring purine nucleosides adenosine, inosine and guanosine were synthesized. Thus, controlled amination of 4 followed by sugar deprotection and dehalogenation yielded the adenosine analog, 4‐amino‐5‐β‐D‐ribofuranosyl‐5H‐pyrrolo[3,2‐d]pyrimidine (8) as the hydrochloride salt. Base hydrolysis of 4 followed by deprotection gave the 2‐chloroinosine analog, 10, and subsequent dehalogenation provided the inosine analog, 5‐β‐D‐ribofuranosyl‐5H‐pyrrolo[3,2‐d]‐pyrimidin‐4(3H)‐one (11). Amination of 10 furnished the guanosine analog, 2‐amino‐5‐β‐D‐ribofuranosyl‐5H‐pyrrolo[3,2‐d]pyrimidin‐4(3H)‐one (12). Finally, the α anomer in the guanosine series, 16, was prepared from 5 by the same procedure as that used to prepare 12. The structural assignments were made on the basis of ultraviolet and proton nmr spectroscopy. In particular, the isopropylidene intermediates 9 and 14 were used to assign the proper configuration as β and α, respectively, according to Imbach's rule.

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Synthesis of Tubercidin, 6-Chlorotubercidin and Related Nucleosides

Cited by 16 publications

References 28 publications

Studies on the Glycosylation of Pyrrolo[2,3-d] Pyrimidines with 1-O-Acetyl-2,3,5-Tri-O-Benzoyl-β-D-Ribofuranose: The Formation of Regioisomers During Toyocamycin and 7-Deazainosine Syntheses

Studies on the Glycosylation of Pyrrolo[2,3-d] Pyrimidines with 1-O-Acetyl-2,3,5-Tri-O-Benzoyl-β-D-Ribofuranose: The Formation of Regioisomers During Toyocamycin and 7-Deazainosine Syntheses

Thiazolo[4,5-d]pyrimidine nucleosides. The synthesis of certain 3-.beta.-D-ribofuranosylthiazolo[4,5-d]pyrimidines as potential immunotherapeutic agents

9‐Deazapurine nucleosides. The synthesis of certain N‐5‐β‐d‐ribofuranosylpyrrolo[3,2‐d]pyrimidines

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