Deoxyadenosine 3 - -3 -, methanolate

C14H20N6O3 CH40 3 -(Cyclobutylamino)-3 -deoxyadenosine, methanolate AMOADB 43 327... 

In the assay described by Amici et al. (1994), a wide variety of pyrimidine and purine nucleoside 5 -monophosphates were separated from their nucleosides by chromatography on a Supelco LClg guard column (4.6 mm x 20 mm, 5 fim). The short column allows separations in less than a minute. The mobile phase was 0.1 M potassium phosphate buffer (pH 6.0) except in the case of adenosine and deoxyadenosine, when 5% methanol was also included. The flow rate was 2 mL/min. Compounds were detected by monitoring the effluent at 254 nm, although sensitivity could be improved in some cases by using a different wavelength. 

The use of 2-deoxyribose derivatives tends to produce anomeric mixtures of nucleosides. Thus 3,5-di-0-p-nitrobenzoyl-2-deoxy-D-ribofuranosyl chloride and JV -benzoyladenine and molecular sieves gave, after deblocking with methanolic barium methoxide, a mixture of the anomeric 2 -deoxyadenosines (b-68MI40901, p. 183). A variation to this technique includes the condensation of JV -benzoylchloromercurioadenine with 5-0-benzoyl-2-deoxy-D-eryf/iro-pentose diisopropyl dithioacetal in acetonitrile under reflux over 4 hours to produce the same anomeric mixture of 2 -deoxyadenosines (B-68MI40901,p. 132). 

Treatment of 6-chloro-9-(2-deoxy-3,5-di-0-(4-toluoyl)-/(-D-ribofuranosyl)purine with methanolic ammonia results in the deprotection of the glyconic moiety with concomitant nucleophilic displacement of the 6-chloro substituent to give 2 -deoxyadenosine (7), ... 

In the laboratory of R.A. Jones, A/ -methoxy derivatives of adenosine and 2 -deoxyadenosine were found to undergo a facile Dimroth rearrangement The high-yielding process allowed the efficient synthesis of [1,7- N2]- and [1,7, NH2- N3] adenosine and 2 -deoxyadenosine that are important tools in the NMR studies of nucleic acid structure and interactions. The rearrangement was carried out in weakly acidic refluxing methanol. 

An excellent separation of five DNA nucleotides (2 -deoxyguanosine, 2 -deoxy-5-methylcytidine, 2 -deoxycytidine, 2 -deoxyadenosine) and their five sulfur mustard adducts (products fixim alleged mustard gas exposure) was generated on a C g column using a complex 40-min 0/100 ->48/52 methanol/water (25 mM ammonium carbonate buffer at pH 8) gradient [442]. Excellent peak shapes and resolution were obtained. 

Two sets of syn- and anft-enantiomers of four 5,6-dimethylchrysene-l,2-dihy-drodiol-3,4-epoxide adducts of both deoxyadenosine and deoxyguanosine were baseline resolved in l.Sh using a C g column (A = 262nm) and a 40/60 - 56/44 methanol/water gradient [446]. Excellent peak shapes were obtained. 

The deoxyadenosine and deoxyguanosine adducts of syn-benzo[g]chrysene-11,12-dihydrodiol-13,14-epoxide were baseline resolved on a Cjg column (A = 264nm) with a 50-min 25/75/0 - 12/60/28 acetonitrile/water/methanol gradient [943]. The R and S conformational adducts were separated individually using a 24/76 acetonitrile/water mobile phase. Elution required nearly 120 min in all cases and peaks were quite tailed. 

Reduction of 113 (B=Thy) and deprotection led to 3 -deoxy-3 -hydroxymethylthymidine, a potent antiviral and antitumour agent, and similar work was done in the deoxyadenosine and deoxyguanosine systems. 3 Photolysis of the chiral cyclobutanone 114 in the presence of 6-chloropurine gave the nucleoside 115, in a novel approach to this system. A full account has been given of the use of the photoaddidon of methanol to butenolides as a route to 2, 3 -dideoxy> 3 -hydroxymethyl nucleosides (see Vol. 26, p. 242). 38... 

Azhayev et al. (74) described the synthesis of 3 -azido-3 -deoxyadenosine and 3 -amino-3 deoxy-adenosine and 15+ intermediates with obtained using ready-for-use Silufol U Vjs4 silica gel sheets in the solvent systems chloroform-methanol (95 5), benzene-ethyl acetate (17 3), benzene-ethyl acetate (4 1) and l-butoanol-H20 (85 15). 

Treatment of the 4 -ene with MCPBA in methanol led to the 4 -methoxy-derivative 212 of d4T, and 4 -methoxy-2 -deoxyadenosine was made in a similar way. 20... 

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