Formaldehyde → 5'-O-(t-Butyldimethylsilyl)-3'-Deoxy-3'-[(Methyleneamino)oxy]thymidine

HRID 54635Notes

Reaction equation

HRID 54635 reaction equation
[CH2:1]=O.[NH2:3][O:4][C@@H:5]1[C@@H:9]([CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[O:8][C@@H:7]([N:19]2[CH:27]=[C:25]([CH3:26])[C:23](=[O:24])[NH:22][C:20]2=[O:21])[CH2:6]1>CO>[Si:12]([O:11][CH2:10][C@H:9]1[O:8][C@@H:7]([N:19]2[CH:27]=[C:25]([CH3:26])[C:23](=[O:24])[NH:22][C:20]2=[O:21])[CH2:6][C@@H:5]1[O:4][N:3]=[CH2:1])([C:15]([CH3:18])([CH3:16])[CH3:17])([CH3:13])[CH3:14]

Participants

4

Reactant 2

HCID 712Formaldehyde2×HCID 186587053'-O-Amino-5'-O-(t-Butyldimethylsilyl)thymidine

Product 1

HCID 228586505'-O-(t-Butyldimethylsilyl)-3'-Deoxy-3'-[(Methyleneamino)oxy]thymidineYield 95%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of HCHO (20% aqueous, 1 ml) was added dropwise to a stirred solution of 3'-O-amino-5'-O-(t-butyldimethylsilyl)thymidine (3, 7.42 g, 20 mmol) in dry MeOH (400 ml) at room temperature. After 6 h, another portion of HCHO (20% aqueous, 1.5 ml) was added and stirring continued for 16 h. The resulting solution was evaporated under reduced pressure, and the residue was purified by chromatography on silica gel to give compound 10 (7.25 g, 95%) as clear foam. 1H NMR (CDCl3) δ0.1 [s, 3, (CH3)2 ], 0.9 [s, 9, (CH3)3 ], 1.9 (s, 3, CH3), 2.25-2.72 (m, 2, 2' CH2), 3.85-4.15 (2m, 3, 5' CH2, 4'H), 4.85 (m, 1, 3'H), 6.25 (dd, 1, 1'H), 6.5 and 6.95 (2d, 2, N=CH2), 7.43 (s, 1, (6H), 9.2 (br s, 1 NH).

Workup

  1. waitcontinued for 16 h
  2. customThe resulting solution was evaporated under reduced pressure
  3. customthe residue was purified by chromatography on silica gel

Sources & evidence

ORD record
ord-b7a379320a4145be89d23d9e3e9b13c5
Source dataset
uspto-grants-1997_04
Patent number
US05623070

Reaction notes

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