Thymine → HCID 57867410, compound

HRID 1516275Notes

Reaction equation

HRID 1516275 reaction equation
[NH:1]1[CH:9]=[C:7]([CH3:8])[C:5](=[O:6])[NH:4][C:2]1=[O:3].C/C(/O[Si](C)(C)C)=N\[Si](C)(C)C.[C:22]([O:30][CH2:31][C@@H:32]1[C:36]([O:38][C:39](=[O:41])[CH3:40])([CH3:37])[C@:35]([F:43])([CH3:42])[CH:34](OC(=O)C)[O:33]1)(=[O:29])[C:23]1C=CC=CC=1.Cl[Sn](Cl)(Cl)Cl.C(=O)(O)[O-].[Na+]>C(#N)C>[C:22]([O:30][CH2:31][C@@H:32]1[C:36]([O:38][C:39](=[O:41])[CH3:40])([CH3:37])[C@:35]([F:43])([CH3:42])[CH:34]([N:1]2[CH:9]=[C:7]([CH3:8])[C:5](=[O:6])[NH:4][C:2]2=[O:3])[O:33]1)(=[O:29])[CH3:23]

Participants

7

Reactant 5

HCID 1135ThymineHCID 24287Tin tetrachlorideHCID 516892Sodium BicarbonateHCID 6913588N,O-bis(trimethylsilyl)acetamideHCID 57867364HCID 57867364, compound

Product 1

HCID 57867410HCID 57867410, compoundYield 30.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

To a stirred solution of thymine (about 0.31 g, 2.48 mmol) in acetonitrile (about 6 ml) was added N,O-Bis(trimethylsilyl)acetamide at room temperature (about 3.6 ml, 16.3 mmol) and refluxed for about 2 hours. To this added ((2R,4R)-3,5-diacetoxy-4-fluoro-3,4-dimethyl-tetrahydrofuran-2-yl)methyl benzoate (about 0.38 gm, 1.24 mmol) in acetonitrile (about 6 ml) drop wise at about 0° C., and added SnCl4 (about 0.2 ml, 1.86 mmol) then refluxed for about 15 hours. Completion of the reaction mixture monitored by thin-layer chromatography and neutralized the reaction mixture with saturated sodium bicarbonate solution. Aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with brine, dried over sodium sulphate. Concentration under reduced pressure and purification by silica gel column chromatography using 60% ethyl acetate/hexane as eluent furnished title compound (0.14 g) as a colorless solid. Yield: 30%; 1H-NMR: 1H NMR (300 MHz, CDCl3): δ 8.22 (s, 1H), 7.13-7.12 (m, 1H), 6.34 (d, 1H, J=23.4 Hz), 4.59-4.50 (m, 2H), 4.16-4.09 (m, 1H), 2.94 (d, 3H, J=22.2 Hz), 2.12 (s, 3H), 1.95 (s, 3H), 1.77 (d, 3H, J=2.4 Hz), 1.55 (d, 3H, J=30 Hz); ES Mass: [M+1] 373 (10%), [M+Na] 395 (100%).

Workup

  1. temperaturerefluxed for about 2 hours
  2. temperaturethen refluxed for about 15 hours
  3. extractionAqueous layer was extracted with ethyl acetate
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried over sodium sulphate
  6. concentrationConcentration
  7. customunder reduced pressure and purification by silica gel column chromatography

Sources & evidence

ORD record
ord-6ae0755f3f9946ab81ae0349dc2db8e2
Source dataset
uspto-grants-2012_07
Patent number
US08227431B2

Reaction notes

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