9-(2-O-acetyl-3,5-di-O-benzoyl-beta-L-xylofuranosyl)adenine → (2s,3r,5s)-5-(6-Amino-9h-Purin-9-Yl)-Tetrahydro-2-(Hydroxymethyl)furan-3-Ol

HRID 1358221Notes

Reaction equation

HRID 1358221 reaction equation
C(O[C@H:5]1[C@H:9]([O:10]C(=O)C2C=CC=CC=2)[C@H:8]([CH2:19][O:20]C(=O)C2C=CC=CC=2)[O:7][C@@H:6]1[N:29]1[CH:37]=[N:36][C:35]2[C:30]1=[N:31][CH:32]=[N:33][C:34]=2[NH2:38])(=O)C>C(O)(=O)C>[CH2:5]1[C@@H:6]([N:29]2[C:30]3[N:31]=[CH:32][N:33]=[C:34]([NH2:38])[C:35]=3[N:36]=[CH:37]2)[O:7][C@@H:8]([CH2:19][OH:20])[C@@H:9]1[OH:10]

Participants

3

Reactant 1

HCID 104366059-(2-O-acetyl-3,5-di-O-benzoyl-beta-L-xylofuranosyl)adenine

Product 1

HCID 489519(2s,3r,5s)-5-(6-Amino-9h-Purin-9-Yl)-Tetrahydro-2-(Hydroxymethyl)furan-3-OlYield 85.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Compound 2 (0.44 g, 0.56 mmol) was treated with an aqueous solution of acetic acid 80% (17 mL) at room temperature for 5 h. The mixture was concentrated to dryness, the residue was dissolved in water (20 mL) and washed with diethyl ether (2×15 mL). The aqueous layer was concentrated and co-evaporated with toluene and methanol. The desired 2′-deoxy-β-L-adenosine (β-L-dA) (0.12 g, 83%) was obtained after purification by silica gel column chromatography (0-12% MeOH in dichloromethane) and filtration through a Millex HV-4 unit (0.45μ, Millipore): mp 193-194° C. (crystallized from water) (Lit. 184-185° C. for L-enantiomer [Ref.: Robins, M. J.; Khwaja, T. A.; Robins, R. K. J Org Chem 1970, 35, 636-639] and 187-189° C. for D-enantiomer [Ref.: Ness, R. K. in Synthetic Procedures in Nucleic Acid Chemistry; Zorbach, W. W., Tipson, R. S., Eds.; J. Wiley and sons: New York, 1968; Vol 1, 183-187]; 1H NMR (DMSO-d6): δ2.2-2.3 and 2.6-2.7 (2m, 2H, H-2′ and H-2″), 3.4-3.6 (2m, 2H, H-5′ and H-5″), 3.86 (pq, 1H, H-4′), 4.3-4.4 (m, 1H, H-3′), 5.24 (t, 1H, OH-5′, JH,OH=5.8 Hz), 5.30 (d, 1H, OH-3′, JH,OH=4.0 Hz), 6.32 (dd, 1H, H-1′, J1′2′=6.2 Hz, J1′,2″=7.8 Hz), 7.3 (br s, 2H, NH2-6), 8.11 and 8.32 (2s, 2H, H-2 and H-8); ms: matrix G/T, (FAB+) m/z 252 [M+H]+, 136 [BH2]+, (FAB−) m/z 250 [M−H]−, 134 [B]−; UV (95% ethanol): λmax 258 nm (ε14300), λmin 226 nm (ε2100); [α]D20=+25 (c 1.03, H2O), (Lit. [α]D20=+23 (c 1.0, H2O) for L-enantiomer [Ref.: Robins, M. J.; Khwaja, T. A.; Robins, R. K. J Org Chem, 1970, 35, 636-639] and [α]D20=−25 (c 0.47, H2O) for D-enantiomer [Ref.: Ness, R. K. in Synthetic Procedures in Nucleic Acid Chemistry; Zorbach, W. W., Tipson, R. S., Eds.; J. Wiley and sons: New York, 1968; Vol 1, 183-187]). Anal. Calcd for C10H13N5O3+1.5 H2O (M=278.28): C, 43.16; H, 5.80; N, 25.17. Found: C, 43.63; H, 5.45; N, 25.33.

Workup

  1. concentrationThe mixture was concentrated to dryness
  2. dissolutionthe residue was dissolved in water (20 mL)
  3. washwashed with diethyl ether (2×15 mL)
  4. concentrationThe aqueous layer was concentrated and co-evaporated with toluene and methanol

Sources & evidence

ORD record
ord-b3e6fbf0d3224874b7064d317c651470
Source dataset
uspto-grants-2003_07
Patent number
US06596700B2

Reaction notes

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