Sodium Thiosulfate → (2R)-2-Allyloxycarbonylamino-2-methyl-4-[5-(4-cyclohexyloxybut-1-ynyl)furan-2-yl]-1-butyl diallyl phosphate

HRID 562616Notes

Reaction equation

HRID 562616 reaction equation
[CH2:1]([O:4][C:5]([NH:7][C@:8]([CH3:29])([CH2:11][CH2:12][C:13]1[O:14][C:15]([C:18]#[C:19][CH2:20][CH2:21][O:22][CH:23]2[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24]2)=[CH:16][CH:17]=1)[CH2:9][OH:10])=[O:6])[CH:2]=[CH2:3].N1C=NN=N1.C(N(C(C)C)[P:39]([O:44][CH2:45][CH:46]=[CH2:47])[O:40][CH2:41][CH:42]=[CH2:43])(C)C.ClC1C=CC=C(C(OO)=[O:59])C=1.S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl>[P:39]([O:40][CH2:41][CH:42]=[CH2:43])([O:44][CH2:45][CH:46]=[CH2:47])([O:10][CH2:9][C@@:8]([NH:7][C:5]([O:4][CH2:1][CH:2]=[CH2:3])=[O:6])([CH3:29])[CH2:11][CH2:12][C:13]1[O:14][C:15]([C:18]#[C:19][CH2:20][CH2:21][O:22][CH:23]2[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24]2)=[CH:16][CH:17]=1)=[O:59]

Participants

7

Reactant 5

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 4686855Diallyl diisopropylphosphoramiditeHCID 66673269(2R)-2-Allyloxycarbonylamino-2-methyl-4-[5-(4-cyclohexyloxybut-1-ynyl) furan-2-yl]butan-1-olHCID 178418441HCID 178418441, compound

Product 1

HCID 66672845(2R)-2-Allyloxycarbonylamino-2-methyl-4-[5-(4-cyclohexyloxybut-1-ynyl)furan-2-yl]-1-butyl diallyl phosphateYield 81.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (2R)-2-allyloxycarbonylamino-2-methyl-4-[5-(4-cyclohexyloxybut-1-ynyl)furan-2-yl]butan-1-ol (0.6202 g, 1.54 mmol) obtained in Example (26a) in dichloromethane (15 ml) were added successively 1H-tetrazole (0.7220 g, 10.31 mmol) and diallyl diisopropylphosphoramidite (0.81 ml, 3.06 mmol) with stirring under ice-cooling, and then the reaction mixture was stirred at room temperature for 2 hours. After stirring, to the reaction mixture was added m-chloroperbenzoic acid (content: 70%) (0.7556 g, 3.07 mmol) with stirring under ice cooling, and the resulting mixture was stirred at the same temperature for 10 minutes. After stirring, to the reaction mixture was added 10% aqueous sodium thiosulfate solution to quench the reaction, and the resulting mixture was extracted with dichloromethane. The extract was washed successively with saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. After filtration, the solvent was removed in vacuo, and the residue was purified by chromatography on a silica gel column using admixed solvent of hexane and ethyl acetate (3:2) as the eluent to afford the title compound (0.7049 g, yield: 81%).

Workup

  1. temperaturecooling
  2. stirringthe reaction mixture was stirred at room temperature for 2 hours
  3. stirringAfter stirring, to the reaction mixture
  4. stirringwith stirring under ice cooling
  5. stirringthe resulting mixture was stirred at the same temperature for 10 minutes
  6. stirringAfter stirring, to the reaction mixture
  7. customto quench
  8. customthe reaction
  9. extractionthe resulting mixture was extracted with dichloromethane
  10. washThe extract was washed successively with saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution
  11. dry with materialdried over anhydrous sodium sulfate
  12. filtrationAfter filtration
  13. customthe solvent was removed in vacuo
  14. customthe residue was purified by chromatography on a silica gel column

Sources & evidence

ORD record
ord-d68eead95d244bfea9d90a0975142b39
Source dataset
uspto-grants-2011_11
Patent number
US08067396B2

Reaction notes

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