4-Toluenesulfonyl chloride → 5'-Azidoguanosine

HRID 1587279Notes

Reaction equation

HRID 1587279 reaction equation
NC[C@H]1O[C@@H](N2C3N=C(N)NC(=O)C=3N=C2)C[C@@H]1O.NC[C@H]1O[C@@H](N2C3N=CN=C(O)C=3N=C2)C[C@@H]1O.[C@@H:38]1([N:46]2[C:56]3[N:55]=[C:53]([NH2:54])[NH:52][C:50](=[O:51])[C:49]=3[N:48]=[CH:47]2)[O:45][C@H:42]([CH2:43][OH:44])[C@@H:40]([OH:41])[CH2:39]1.S(Cl)(C1C=CC(C)=CC=1)(=O)=O.S(C1C=CC(C)=CC=1)([O-])(=O)=[O:69].[N-:79]=[N+:80]=[N-:81].[Na+].[N-]=[N+]=[N-].[Li+]>N1C=CC=CC=1.CN(C=O)C>[N:79]([CH:43]([OH:44])[C@H:42]1[O:45][C@@H:38]([N:46]2[C:56]3[N:55]=[C:53]([NH2:54])[NH:52][C:50](=[O:51])[C:49]=3[N:48]=[CH:47]2)[C@H:39]([OH:69])[C@@H:40]1[OH:41])=[N+:80]=[N-:81]

Participants

10

Reactant 7

HCID 73974-Toluenesulfonyl chlorideHCID 33557Sodium AzideHCID 85570p-ToluenesulfonateHCID 88163Lithium azideHCID 135398592DeoxyguanosineHCID 1358167395'-Amino-2',5'-dideoxyguanosineHCID 178511304HCID 178511304, compound

Product 1

HCID 1364033885'-Azidoguanosine

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6228DimethylformamideSolvent2×

Procedure

An alternate preparation of 5'-amino-2',5'-dideoxyguanosine (or 5'-amino-2',5'-dideoxyinosine) is to treat the protected 2'-deoxy guanosine (protected as the N-2-acetyl, the N-2-phenylacetyl, or the N-2-FMOC derivative) (1 mmol) with tosyl chloride (1.3 mmol) in pyridine at 0° C. overnight. The solution is evaporated to dryness and the residue is dissolved in chloroform. The resulting solution is washed twice with aqueous sodium bicarbonate and dried over sodium sulfate. The solvent is evaporated and the residue chromatographed on silica gel eluting with methanol/chloroform mixtures. The resulting tosylate (1 mmol) is treated with sodium azide (6 mmol) in DMF at 80°-100° C. for a few h, or lithium azide (10 mmol) in DMF at 60° C. for several h. The solvent is removed by rotovap and the residue is chromatographed on silica gel eluting with chloroform/methanol solvent mixtures. The azide is reduced to the desired amine using the above procedure.

Workup

  1. customat 0° C.
  2. customovernight
  3. customThe solution is evaporated to dryness
  4. dissolutionthe residue is dissolved in chloroform
  5. washThe resulting solution is washed twice with aqueous sodium bicarbonate
  6. dry with materialdried over sodium sulfate
  7. customThe solvent is evaporated
  8. customthe residue chromatographed on silica gel eluting with methanol/chloroform mixtures
  9. customThe solvent is removed by rotovap
  10. customthe residue is chromatographed on silica gel eluting with chloroform/methanol solvent mixtures

Sources & evidence

ORD record
ord-6b015f7e053948508d21916e286e2077
Source dataset
uspto-grants-1993_06
Patent number
US05217866

Reaction notes

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