Methanol → HCID 15867812, compound

HRID 1604118Notes

Reaction equation

HRID 1604118 reaction equation
FC(F)(F)S(O[C:7]1[CH2:21][C@@H:20]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[C@H:19](/[CH:30]=[CH:31]/[C@@H:32]([O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:43])[CH3:42])[CH2:33][C@H:34]([CH3:39])[CH2:35][CH2:36][CH2:37][CH3:38])[C:8]=1[S:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]([O:17][CH3:18])=[O:16])(=O)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:69][OH:70].C(N(CC)CC)C.CN(C)[CH:80]=[O:81]>[C]=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH3:69][O:70][C:80]([C:7]1[CH2:21][C@@H:20]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[C@H:19](/[CH:30]=[CH:31]/[C@@H:32]([O:40][Si:41]([C:44]([CH3:47])([CH3:45])[CH3:46])([CH3:42])[CH3:43])[CH2:33][C@H:34]([CH3:39])[CH2:35][CH2:36][CH2:37][CH3:38])[C:8]=1[S:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]([O:17][CH3:18])=[O:16])=[O:81]

Participants

9

Reactant 5

HCID 887MethanolHCID 6228DimethylformamideHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 15867790HCID 15867790, compound

Product 1

HCID 15867812HCID 15867812, compoundYield 38%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 178418416HCID 178418416, compoundSolvent

Procedure

Methyl (11R,12S,13E,15S,17R)-9-trifluoromethanesulfonyloxy-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate (388 mg, 0.5 mmol), palladium acetate (11.2 mg, 0.05 mmol), and triphenylphospine (26.2 g, 0.1 mmol) were dissolved in dimethylformamide (2 mL). To this were added methanol (810 μl, 20 mmol) and triethylamine (139 μl, 1 mmol). This was agitated in carbon monoxide atmosphere (1 atmosphere) at room temperature for 18 hours. 10 ml of water was added, the solution separated, and the aqueous phase was extracted with ether and the extract combined with the organic layer. The organic solution was washed with brine, then was dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure, then was purified by silica gel column chromatography (4% ethyl acetate/hexane) to obtain methyl (11R,12S,13E,15S,17R)-9-methoxycarbonyl-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate (134 mg, 38%).

Workup

  1. customthe solution separated
  2. extractionthe aqueous phase was extracted with ether
  3. washThe organic solution was washed with brine
  4. dry with materialwas dried over anhydrous sodium sulfate
  5. concentrationThe solution was concentrated under reduced pressure
  6. customwas purified by silica gel column chromatography (4% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-a72e1cf8cafc48f38d84f84bf2c6c031
Source dataset
uspto-grants-1999_11
Patent number
US05990346

Reaction notes

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