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 1051281Notes

Reaction equation

HRID 1051281 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-d188a0f46d4044f79e3f395bd1d7e6ce
Source dataset
uspto-grants-2016_07
Patent number
US09388157B2

Reaction notes

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