Sodium hydride → (3aR,4R,5R,6aS)-2-Oxo-4-((R,E)-3-oxo-4-(m-tolyl)pent-1-en-1-yl)hexahydro-2H-cyclopenta[b]furan-5-yl benzoate

HRID 2363219Notes

Reaction equation

HRID 2363219 reaction equation
[H-].[Na+].C[CH:4](C)[C@H:5]([C:13]1[CH:14]=[C:15]([CH3:19])[CH:16]=[CH:17][CH:18]=1)[C:6](=[O:12])[CH2:7]P(=O)(O)O.P(=O)(O)O.[CH:25]([C@H:27]1[C@H:34]([O:35][C:36](=[O:43])[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH2:33][C@H:32]2[C@@H:28]1[CH2:29][C:30](=[O:44])[O:31]2)=O>COCCOC>[O:12]=[C:6]([C@@H:5]([C:13]1[CH:14]=[C:15]([CH3:19])[CH:16]=[CH:17][CH:18]=1)[CH3:4])/[CH:7]=[CH:25]/[C@H:27]1[C@H:34]([O:35][C:36](=[O:43])[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH2:33][C@H:32]2[C@@H:28]1[CH2:29][C:30](=[O:44])[O:31]2

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 11000244(3aR,4R,5R,6aS)-4-formyl-2-oxohexahydro-2H-cyclopenta[b]furan-5-yl benzoateHCID 178425040HCID 178425040, compound

Product 1

HCID 67108363(3aR,4R,5R,6aS)-2-Oxo-4-((R,E)-3-oxo-4-(m-tolyl)pent-1-en-1-yl)hexahydro-2H-cyclopenta[b]furan-5-yl benzoateYield 99.6%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent3×

Procedure

Sodium hydride (55%) (8.75 g) was dispersed in 1,2-dimethoxyethane (DME) (300 mL) and the mixture was ice-cooled. A solution of phosphonate (dimethyl (3R)-2-oxo-3-(m-tolyl)butylphosphonate) (54.7 g) synthesized in Example 2 in DME (50 mL) was added, and the mixture was stirred for 1 hr. To the above-mentioned solution was added a solution of (1S,5R,6R,7R)-6-formyl-7-benzoyloxy-2-oxabicyclo[3.3.0]octan-3-one (50.0 g) in DME (400 mL), and the mixture was stirred for 1 hr. The reaction was quenched with 350 mL of 10% brine, and the mixture was extracted with ethyl acetate. The extract was dried over magnesium sulfate, and the residue was concentrated under reduced pressure. The concentrated crude product was recrystallized from t-butyl methyl ether to give the title compound (64.7 g). The structural property was as described below.

Workup

  1. temperaturecooled
  2. stirringthe mixture was stirred for 1 hr
  3. customThe reaction was quenched with 350 mL of 10% brine
  4. extractionthe mixture was extracted with ethyl acetate
  5. dry with materialThe extract was dried over magnesium sulfate
  6. concentrationthe residue was concentrated under reduced pressure
  7. concentrationThe concentrated crude product
  8. customwas recrystallized from t-butyl methyl ether

Sources & evidence

ORD record
ord-5f3b163cfada4fb9963a53d748eefc22
Source dataset
uspto-grants-2014_04
Patent number
US08691857B2

Reaction notes

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