Sodium hydride → (1R,5S,6S,7R)-3,3-Ethylenedioxy-7-benzoyloxy-6-[(4RS)-2-bromo-4-methyl-3-oxooct-1-en-6-ynyl]bicyclo[3.3.0]octane

HRID 466594Notes

Reaction equation

HRID 466594 reaction equation
COP([CH2:7][C:8](=[O:15])[CH:9]([CH3:14])[CH2:10][C:11]#[C:12][CH3:13])(=O)OC.[H-].[Na+].[Br:18]N1C(=O)CCC1=O.[CH2:26]1[CH2:48][O:47][C:28]2([CH2:35][C@H:34]3[C@H:30]([CH2:31][C@@H:32]([O:38][C:39](=[O:46])[C:40]4[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=4)[C@@H:33]3[CH:36]=O)[CH2:29]2)[O:27]1.[Cl-].[NH4+]>C(COC)OC>[CH2:26]1[CH2:48][O:47][C:28]2([CH2:35][C@H:34]3[C@H:30]([CH2:31][C@@H:32]([O:38][C:39](=[O:46])[C:40]4[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=4)[C@@H:33]3[CH:36]=[C:7]([Br:18])[C:8](=[O:15])[CH:9]([CH3:14])[CH2:10][C:11]#[C:12][CH3:13])[CH2:29]2)[O:27]1

Participants

7

Reactant 5

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 67184N-bromobutanimideHCID 110426053-Methyl-2-oxohept-5-ynylphosphonic acid dimethyl esterHCID 13245601(lR,5S,6R,7R)-3,3-ethylenedioxy-7-benzoyloxy-6formylbicyclo [3.3.0]octane

Product 1

HCID 56607337(1R,5S,6S,7R)-3,3-Ethylenedioxy-7-benzoyloxy-6-[(4RS)-2-bromo-4-methyl-3-oxooct-1-en-6-ynyl]bicyclo[3.3.0]octane

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

At 0° C., a solution of 10.5 g of 3-methyl-2-oxohept-5-ynephosphonic acid dimethyl ester in 70 ml of dimethoxyethane is added dropwise to a suspension of 1.81 g of sodium hydride in 180 ml of dimethoxyethane; the mixture is stirred for one hour at 0° C. and then 7.4 g of finely pulverized N-bromosuccinimide is added thereto. The mixture is agitated for 30 minutes at 0° C., combined with a solution of 11.4 g of (1R,5S,6R,7R)-3,3-ethylenedioxy-7-benzoyloxy-6-formylbicyclo[3.3.0]octane in 90 ml of dimethoxyethane, and agitated for 2 hours at 0° C. The reaction mixture is poured on saturated ammonium chloride solution and extracted with ether. The organic extract is washed neutral with water, dried over magnesium sulfate, and evaporated under vacuum. Chromatography of the residue on silica gel yields, with hexane/ether (3+2), 8.2 g of the unsaturated ketone as a colorless oil.

Workup

  1. stirringThe mixture is agitated for 30 minutes at 0° C.
  2. stirringagitated for 2 hours at 0° C
  3. extractionextracted with ether
  4. extractionThe organic extract
  5. washis washed neutral with water
  6. dry with materialdried over magnesium sulfate
  7. customevaporated under vacuum

Sources & evidence

ORD record
ord-449ee6b739044680a6baa7bc0ed95c3d
Source dataset
uspto-grants-1992_10
Patent number
US05157042

Reaction notes

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