Water → 2-propanyl (2E)-3-[(2R,5aR,6S,7R,8aS)-6-({[dimethyl(2-methyl-2-propanyl)silyl]oxy}methyl)-7-(tetrahydro-2H-pyran-2-yloxy)-3,5a,6,7,8,8a-hexahydro-2H-cyclopenta[b]oxepin-2-yl]acrylate

HRID 573529Notes

Reaction equation

HRID 573529 reaction equation
[CH3:1][Si:2]([CH3:28])([C:24]([CH3:27])([CH3:26])[CH3:25])[O:3][CH2:4][C@@H:5]1[C@@H:14]2[C@@H:8]([O:9][C@@H:10]([CH2:15]O)[CH2:11][CH:12]=[CH:13]2)[CH2:7][C@H:6]1[O:17][CH:18]1[CH2:23][CH2:22][CH2:21][CH2:20][O:19]1.OI1(=O)C2C=CC=CC=2[C:32](=O)O1.[C:41]([O:44][CH2:45][CH3:46])(=[O:43])[CH3:42].O>CS(C)=O>[CH3:28][Si:2]([CH3:1])([C:24]([CH3:25])([CH3:26])[CH3:27])[O:3][CH2:4][C@@H:5]1[C@@H:14]2[C@@H:8]([O:9][C@@H:10](/[CH:15]=[CH:42]/[C:41]([O:44][CH:45]([CH3:32])[CH3:46])=[O:43])[CH2:11][CH:12]=[CH:13]2)[CH2:7][C@H:6]1[O:17][CH:18]1[CH2:23][CH2:22][CH2:21][CH2:20][O:19]1

Participants

6

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 3394961-Hydroxy-1,2-benziodoxol-3(1H)-one 1-oxideHCID 68751161HCID 68751161, compound

Product 1

HCID 866653212-propanyl (2E)-3-[(2R,5aR,6S,7R,8aS)-6-({[dimethyl(2-methyl-2-propanyl)silyl]oxy}methyl)-7-(tetrahydro-2H-pyran-2-yloxy)-3,5a,6,7,8,8a-hexahydro-2H-cyclopenta[b]oxepin-2-yl]acrylate

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
50 °C

Procedure

The compound (165 mg) produced in Example 55 was dissolved in DMSO (2 mL), a Wittig reagent (carboisopropoxymethylenetriphenylphosphorane, 218 mg) and 1-hydroxy-1,2-benziodoxol-3(1H)-one 1-oxide (IBX, 168 mg) were added, followed by stirring at 50° C. for 5 hours. Ethyl acetate and water were added to the reaction mixture, and insolubles were filtered. Extraction with ethyl acetate, and washing with an aqueous saturated sodium bicarbonate solution and a saline, and drying with anhydrous magnesium sulfate were carried out, followed by concentration under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=97:3→80:20) to obtain a titled compound (174 mg) having the following physical property values.

Workup

  1. filtrationwere filtered
  2. extractionExtraction with ethyl acetate
  3. washwashing with an aqueous saturated sodium bicarbonate solution
  4. dry with materiala saline, and drying with anhydrous magnesium sulfate
  5. concentrationfollowed by concentration under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=97:3→80:20)

Sources & evidence

ORD record
ord-4d143836b175431bb3d300a54b71c243
Source dataset
uspto-grants-2015_05
Patent number
US09029574B2

Reaction notes

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