tert-Butyl hydroperoxide → HCID 178462427, compound

HRID 1766950Notes

Reaction equation

HRID 1766950 reaction equation
[OH:1][CH2:2][C:3]([O:5][C@:6]([C:35]1[CH:40]=[CH:39][C:38]([F:41])=[CH:37][C:36]=1[F:42])([CH2:29][N:30]1[CH:34]=[N:33][CH:32]=[N:31]1)[C@H:7]([S:9][C@@H:10]1[CH2:15][O:14][C@@H:13](/[CH:16]=[CH:17]/[CH:18]=[CH:19]/[C:20]2[CH:25]=[CH:24][C:23]([C:26]#[N:27])=[CH:22][C:21]=2[F:28])[O:12][CH2:11]1)[CH3:8])=[O:4].N1C=NN=N1.C([O:51][P:52]([O:60]CC=C)N(C(C)C)C(C)C)C=C.C([O:68]O)(C)(C)C.C(=O)([O-])O.[Na+:74].S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl.CO>[P:52]([O-:60])([O:1][CH2:2][C:3]([O:5][C@:6]([C:35]1[CH:40]=[CH:39][C:38]([F:41])=[CH:37][C:36]=1[F:42])([CH2:29][N:30]1[CH:34]=[N:33][CH:32]=[N:31]1)[C@H:7]([S:9][C@@H:10]1[CH2:11][O:12][C@@H:13](/[CH:16]=[CH:17]/[CH:18]=[CH:19]/[C:20]2[CH:25]=[CH:24][C:23]([C:26]#[N:27])=[CH:22][C:21]=2[F:28])[O:14][CH2:15]1)[CH3:8])=[O:4])([OH:68])=[O:51].[Na+:74]

Participants

9

Reactant 6

HCID 6410tert-Butyl hydroperoxideHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 4686855Diallyl diisopropylphosphoramiditeHCID 178418441HCID 178418441, compoundHCID 178462426HCID 178462426, compound

Product 1

HCID 178462427HCID 178462427, compoundYield 84%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of (1R,2R)-2-[[trans-2-[(1E,3E)-4-(4-cyano-2-fluorophenyl)-1,3-butadienyl]-1,3-dioxan-5-yl]thio]-1-(2,4-difluorophenyl)-1-[(1H-1,2,4-triazol-1-yl)methyl]propyl 2-hydroxyacetate (343.2 mg, 0.571 mmol) obtained from Example 39 in dichloromethane (10 ml) was cooled to 0° C., and to the solution were added tetrazole (80.1 mg, 1.15 mmol) and bis(allyloxy)(diisopropylamino)phosphine (described in Tetrahedron Lett., 30, 4219, (1989); 182.1 mg, 0.742 mmol). The mixture was stirred at the same temperature for 20 minutes. To the mixture was added methanol (0.1 ml), and the mixture was stirred for 5 minutes. To the mixture was added tert-butyl hydroperoxide (80% di-tert-butyl hydroperoxide solution; 0.27 g, 2.4 mmol) at 0° C., and the mixture was stirred at room temperature for 15 minutes. To the mixture were added a saturated aqueous solution of sodium hydrogen carbonate and a solution of sodium thiosulfate, and the mixture was stirred for 10 minutes. At the end of this time, the product was extracted with ethyl acetate, and the solvent was removed under reduced pressure. The resulting oily residue was purified by column chromatography using silica gel (20 g; eluent, ethyl acetate:hexane=4:1), to give the title compound (365.4 mg, yield 84%) as a pale brown amorphous solid.

Workup

  1. stirringthe mixture was stirred for 5 minutes
  2. stirringthe mixture was stirred at room temperature for 15 minutes
  3. extractionAt the end of this time, the product was extracted with ethyl acetate
  4. customthe solvent was removed under reduced pressure
  5. customThe resulting oily residue was purified by column chromatography

Sources & evidence

ORD record
ord-71742c2c37a442518cba7cfdf90fbdb7
Source dataset
uspto-grants-2007_06
Patent number
US07230023B2

Reaction notes

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