Ammonia → (2R,3R,4S,5R)-2-(2-amino-5,6-dichloro-benzimidazol-1-yl)-5-(hydroxymethyl)tetrahydrofuran-3,4-diol

HRID 263872Notes

Reaction equation

HRID 263872 reaction equation
Cl[C:2]1[N:6]([C@@H:7]2[O:19][C@H:18]([CH2:20][O:21]C(=O)C)[C@@H:13]([O:14]C(=O)C)[C@H:8]2[O:9]C(=O)C)[C:5]2[CH:25]=[C:26]([Cl:30])[C:27]([Cl:29])=[CH:28][C:4]=2[N:3]=1.[NH3:31]>CO>[NH2:31][C:2]1[N:6]([C@@H:7]2[O:19][C@H:18]([CH2:20][OH:21])[C@@H:13]([OH:14])[C@H:8]2[OH:9])[C:5]2[CH:25]=[C:26]([Cl:30])[C:27]([Cl:29])=[CH:28][C:4]=2[N:3]=1

Participants

4

Reactant 2

HCID 222Ammonia2×HCID 466019[(2R,3R,4R,5R)-3,4-diacetoxy-5-(2,5,6-trichlorobenzimidazol-1-yl)tetrahydrofuran-2-yl]methyl acetate

Product 1

HCID 466018(2R,3R,4S,5R)-2-(2-amino-5,6-dichloro-benzimidazol-1-yl)-5-(hydroxymethyl)tetrahydrofuran-3,4-diol

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

2,5,6-Trichloro-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)benzimidazole (42, 0.48 g; 1 mmole) was dissolved in dry MeOH (10 ml). Liq. NH3 (10 ml) was added and the mixture heated in a steel bomb at 100° C. for 2 hr. This mixture was stirred at room temperature for 24 hr. Excess NH3 was allowed to evaporate and the solution evaporated to dryness, absorbed onto silica gel (2 g), and chromatographed on a silica gel column using silica gel (20 g; 60-200 mesh). Elution of the column with CH2Cl2 :CH3OH (96:4) gave the desired compound 44 as the major nucleoside. Evaporation of the solvent and crystallization of the residue from EtOH gave 44 (0.02 g; yield 6.06%). mp. 145° C.; UV Imax. (MeOH): 259 (7941) and 301 (8348) nm; Imax (pH1): 215 (26000) and 292 (7520) nm; Imax (pH11): 257 (7967) and 298 (7107) nm; 1H NMR(DMSO-d6): d 8.70 (s,1H, C7 -H, 8.28(s,1H, C4 -H), 7.90 (bs,2H, D2O exchangeable, NH2), 6.75(d,C1'H, J1,2 =4.5 Hz) and the rest of the sugar protons.

Workup

  1. customto evaporate
  2. customthe solution evaporated to dryness
  3. customabsorbed onto silica gel (2 g)
  4. customchromatographed on a silica gel column
  5. washElution of the column with CH2Cl2 :CH3OH (96:4)

Sources & evidence

ORD record
ord-9354c40e84184c13baf8fd16fbcdeb4f
Source dataset
uspto-grants-1997_07
Patent number
US05646125

Reaction notes

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