5-Fluorouracil → [(2S,3S,4S,5S)-3,4-dibenzoyloxy-5-(5-fluoro-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl benzoate

HRID 744162Notes

Reaction equation

HRID 744162 reaction equation
[F:1][C:2]1[C:3](=[O:9])[NH:4][C:5](=[O:8])[NH:6][CH:7]=1.C(O[C@H:14]1[O:36][C@@H:35]([CH2:37][O:38][C:39](=[O:46])[C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[C@H:25]([O:26][C:27](=[O:34])[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@@H:15]1[O:16][C:17](=[O:24])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)(=O)C.C[Si](N[Si](C)(C)C)(C)C.Cl[Si](C)(C)C.Cl[Sn](Cl)(Cl)Cl>CC#N>[C:17]([O:16][C@H:15]1[C@@H:25]([O:26][C:27](=[O:34])[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@H:35]([CH2:37][O:38][C:39](=[O:46])[C:40]2[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=2)[O:36][C@@H:14]1[N:6]1[CH:7]=[C:2]([F:1])[C:3](=[O:9])[NH:4][C:5]1=[O:8])(=[O:24])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

7

Reactant 5

HCID 33855-FluorouracilHCID 6397ChlorotrimethylsilaneHCID 13838HexamethyldisilazaneHCID 24287Tin tetrachlorideHCID 10973190Ribofuranose, 1-acetate 2,3,5-tribenzoate

Product 1

HCID 13827065[(2S,3S,4S,5S)-3,4-dibenzoyloxy-5-(5-fluoro-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl benzoateYield 61.9%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a mixture of 5-fluorouracil (0.85 g, 6.54 mmol) and compound 2 (3.0 g, 5.94 mmol) in anhydrous MeCN (100 ml) were successively added HMDS (1.25 ml, 5.95 mmol), ClSiMe3 (0.6 ml, 4.76 mmol) and SnCl4 (0.83 ml, 7.13 mmol). The resulting clear solution was refluxed for 1 hour when TLC indicated completion of the reaction. The solvent was evaporated and the residue dissolved in EtOAc (250 ml), washed with NaHCO3 and H2O. The EtOAc layer was dried, filtered and evaporated to give a white solid and it was crystallized from CHCl3 /MeOH (1-2%) to give compound 5 (2.11 g, 61.9%) as white crystals: m.p. 208°-209° C.

Workup

  1. temperatureThe resulting clear solution was refluxed for 1 hour when TLC
  2. customcompletion of the reaction
  3. customThe solvent was evaporated
  4. dissolutionthe residue dissolved in EtOAc (250 ml)
  5. washwashed with NaHCO3 and H2O
  6. dry with materialThe EtOAc layer was dried
  7. filtrationfiltered
  8. customevaporated
  9. customto give a white solid and it
  10. customwas crystallized from CHCl3 /MeOH (1-2%)

Sources & evidence

ORD record
ord-53dcae0d336b4abab98031f746b383bc
Source dataset
uspto-grants-1996_09
Patent number
US05559101

Reaction notes

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