Diethyl Ether → HCID 131722977, compound

HRID 428817Notes

Reaction equation

HRID 428817 reaction equation
[Cu]C#N.[OH:4][C:5]([CH3:26])([CH2:22][CH2:23][CH2:24][CH3:25])[CH2:6]/[CH:7]=[CH:8]/[Sn](CCCC)(CCCC)CCCC.C(OCC)C.C[Li].[Si:34]([O:41][CH:42]1[CH2:46][C:45](=[O:47])[C:44]([CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][C:54]([O:56][CH3:57])=[O:55])=[CH:43]1)([C:37]([CH3:40])([CH3:39])[CH3:38])([CH3:36])[CH3:35].[Cl-].[NH4+]>O1CCCC1>[CH3:57][O:56][C:54](=[O:55])[CH2:53][CH2:52][CH2:51][CH2:50][CH2:49][CH2:48][C@@H:44]1[C@@H:43](/[CH:8]=[CH:7]/[CH2:6][C:5]([OH:4])([CH3:26])[CH2:22][CH2:23][CH2:24][CH3:25])[CH:42]([O:41][Si:34]([C:37]([CH3:40])([CH3:39])[CH3:38])([CH3:35])[CH3:36])[CH2:46][C:45]1=[O:47]

Participants

8

Reactant 6

HCID 3283Diethyl EtherHCID 25517Ammonium ChlorideHCID 4653916Methyl 7-(3-((tert-butyldimethylsilyl)oxy)-5-oxocyclopent-1-en-1-yl)heptanoateHCID 11026395HCID 11026395, compoundHCID 178418348HCID 178418348, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 131722977HCID 131722977, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Into a dry flask were placed copper (I) cyanide (10.6 g, 118 mmol) and a solution of [(4RS, 1E)-4-hydroxy-4-methyl-1-octenyl]tri-n-butyltin (58.4 g, 135 mmol) in dry tetrahydrofuran (600 ml) under nitrogen atmosphere, and the mixture was cooled to 0° C. To this mixture was dropped 360 ml (389 mmol) of a diethyl ether solution of methyllithium (1.08 mol/liter), and stirring was continued for 1 h, letting the temperature rise gradually to room temperature. After cooling to −78° C., a solution of (±) methyl 7-(3-tert-butyldimethylsilyloxy-5-oxo-1-cyclopentenyl)heptanoate (30.0 g, 84.6 mmol) in dry tetrahydrofuran (140 ml) was rapidly added. After stirring for 5 min, 300 ml of a saturated aqueous ammonium chloride/aqueous ammonia (9:1) was added, and stirring was continued for 30 min , letting the temperature rise gradually to room temperature. This mixture was extracted with ethyl acetate (400 ml) two times, and the combined organic layer was washed with a saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and concentrated in vacuo to remove solvent. The residue was purified by silica gel column chromatography [ethyl acetate/hexane (1/5)] to give 39.5 g (94% yield) of (±)-methyl(16RS, 13E)-11-tert-butyldimethylsilyloxy-16-hydroxy-16-methyl-9-oxoprost-13-en-1-oate as a colorless oil. The spectral data of IR and 1H NMR were identical with those of the example 2.

Workup

  1. customInto a dry flask were placed
  2. customgradually to room temperature
  3. stirringAfter stirring for 5 min
  4. stirringstirring
  5. waitwas continued for 30 min
  6. customgradually to room temperature
  7. extractionThis mixture was extracted with ethyl acetate (400 ml) two times
  8. washthe combined organic layer was washed with a saturated aqueous sodium chloride
  9. dry with materialdried over anhydrous magnesium sulfate
  10. concentrationconcentrated in vacuo
  11. customto remove solvent
  12. customThe residue was purified by silica gel column chromatography [ethyl acetate/hexane (1/5)]

Sources & evidence

ORD record
ord-bd593455bcb44fe3980b4649e1e15d06
Source dataset
uspto-grants-2001_11
Patent number
US06313341B1

Reaction notes

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