Formic Acid → HCID 15867810, compound

HRID 1604117Notes

Reaction equation

HRID 1604117 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.C(O)=O.[CH3:72][OH:73].[O-][Si]([O-])=O.[Mg+2]>O1CCCC1.CN(C)C=O.[C]=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(N(CC)CC)C>[CH:72]([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]([CH3:45])([CH3:46])[CH3:47])([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:73]

Participants

11

Reactant 5

HCID 284Formic AcidHCID 887MethanolHCID 11776TriphenylphosphineHCID 61680MAGNESIUM SILICATE (synthetic)HCID 15867790HCID 15867790, compound

Product 1

HCID 15867810HCID 15867810, compound

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent2×HCID 178418416HCID 178418416, compoundSolvent2×

Conditions

Temperature
80 °C

Procedure

Methyl (11R,12S,13E,15S,17R)-9-trifluoromethanesulfonyloxy-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate (120 mg, 0.154 mmol), palladium acetate (11.2 mg, 0.05 mmol), triphenylphosphine (26 mg, 0.1 mmol), formic acid (12 μl, 0.309 mmol), and triethylamine (65 μl, 063 mmol) in tetrahydrofuran (6 mL) were placed in an autoclave into which carbon monoxide gas was pumped under pressure to give the internal pressure of 17 atmospheres. The solution was heated and agitated at 80° C. for 15 hours. This was dissolved in dimethylformamide (2 ml). Methanol (810 μl, 20 mmol) and triethylamine (139 μl, 1 mmol) were added. This was agitated in carbon monoxide atmosphere (1 atmosphere) at room temperature for further 18 hours. The reaction vessel was cooled to room temperature, then carbon monoxide in the reaction vessel was removed, the reaction solution thus obtained was passed through Florisil column, was concentrated under reduced pressure, and was purified by silica gel column chromotography (2 to 5% ethyl acetate/hexane) to obtain methyl (11R,12S,13E,15S,17R)-9-formyl-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate as a crude (21 mg).

Workup

  1. customto give the internal pressure of 17 atmospheres
  2. temperatureThe solution was heated
  3. temperatureThe reaction vessel was cooled to room temperature
  4. customcarbon monoxide in the reaction vessel was removed
  5. customthe reaction solution thus obtained
  6. concentrationwas concentrated under reduced pressure
  7. customwas purified by silica gel column chromotography (2 to 5% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-a36b000dd70e4381916fe30a4509a1ae
Source dataset
uspto-grants-1999_11
Patent number
US05990346

Reaction notes

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