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 1855677Notes

Reaction equation

HRID 1855677 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, and the mixture was stirred at 50° C. for 5 hours. To the reaction mixture were added ethyl acetate and water, and insolubles were filtered. The filtrate was extracted with ethyl acetate, and the extract was washed with an aqueous saturated sodium bicarbonate solution and a saline, dried with anhydrous magnesium sulfate, and concentrated 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. extractionThe filtrate was extracted with ethyl acetate
  3. washthe extract was washed with an aqueous saturated sodium bicarbonate solution
  4. dry with materiala saline, dried with anhydrous magnesium sulfate
  5. concentrationconcentrated 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-5b6afa3baa3c40a9bb12a2b7682f28cf
Source dataset
uspto-grants-2015_02
Patent number
US08962868B2

Reaction notes

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