Sodium hydride → HCID 10970223, compound

HRID 727468Notes

Reaction equation

HRID 727468 reaction equation
[H-].[Na+].[Si:3]([O:10][C@@H:11]1[C@@H:15]([CH:16]([CH:18]=O)O)[O:14][C@@H:13]([N:20]2[CH:28]=[C:26]([CH3:27])[C:24](=[O:25])[NH:23][C:21]2=[O:22])[CH2:12]1)([C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:5])[CH3:4]>CS(C)=O.[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(OCC)(=O)C>[Si:3]([O:10][C@@H:11]1[C@@H:15]([CH:16]=[CH2:18])[O:14][C@@H:13]([N:20]2[CH:28]=[C:26]([CH3:27])[C:24](=[O:25])[NH:23][C:21]2=[O:22])[CH2:12]1)([C:6]([CH3:7])([CH3:8])[CH3:9])([CH3:5])[CH3:4]

Participants

6

Reactant 2

HCID 24758Sodium hydrideHCID 22881712HCID 22881712, compound

Product 1

HCID 10970223HCID 10970223, compound

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 679Dimethyl SulfoxideSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

A suspension of sodium hydride (60% in mineral oil, 2.88 g, 72 mmol) in anhydrous DMSO (100 ml) after stirring at 65° C. for 1.5 h under nitrogen was changed to a clear solution, which was cooled to room temperature and transferred to a cold, stirred suspension of methyltriphenylphosphonium bromide (27.0 g, 75.6 mmol) in DMSO (20 ml) under nitrogen. The reaction mixture was stirred at room temperature for 45 min. and a solution of 3'-O-t-butyldimethylsilyl-5'-formylthymidine (8.50 g, 24 mmol) in DMSO (40 ml) added with cooling. The reaction mixture was stirred at room temperature for 2 h, diluted with ethyl acetate (2 L), washed with brine (5×800 ml), dried (Na2SO4), concentrated. The crude was purified by chromatography on silica (EtOAc-hexane, 30:70) to give 6.79 g (80.2%) of 3'-O-t-butyldimethylsilyl-5'-deoxy-5'-methylidenethymidine as a colorless solid, m.p. 122° (recrystalization from ethyl acetate and hexane).

Workup

  1. temperaturewas cooled to room temperature
  2. stirringstirred
  3. stirringThe reaction mixture was stirred at room temperature for 45 min.
  4. temperaturewith cooling
  5. stirringThe reaction mixture was stirred at room temperature for 2 h
  6. washwashed with brine (5×800 ml)
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated
  9. customThe crude was purified by chromatography on silica (EtOAc-hexane, 30:70)
  10. customto give
  11. custom6.79 g (80.2%) of 3'-O-t-butyldimethylsilyl-5'-deoxy-5'-methylidenethymidine as a colorless solid, m.p. 122° (recrystalization from ethyl acetate and hexane)

Sources & evidence

ORD record
ord-c43654736c7c4a5889063638e716c836
Source dataset
uspto-grants-1998_01
Patent number
US05712378

Reaction notes

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