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Citric Acid → (1S,5R,6R,7R)-6-(3-oxo-5-phenyl-1E-pentenyl)-7-((4-phenylbenzoyl)oxy)-2-oxabicyclo(3.3.0)octan-3-one

HRID 1375234
Notes
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Reaction equation

HRID 1375234 reaction equation
[CH2:1]1[C@@H:9]([O:10][C:11]([C:13]2[CH:18]=[CH:17][C:16]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[CH:15][CH:14]=2)=[O:12])[C@H:8]([CH2:25]O)[C@H:3]2[CH2:4][C:5]([O:7][C@@H:2]12)=[O:6].[Na+].[Br-].C([O-])(O)=O.[Na+].CC(O)C.[O-]Cl.[Na+].[C:41]1([CH2:47][CH2:48][C:49]([CH2:51]P(OC)(OC)=O)=[O:50])[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1.[OH-].[Na+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C(Cl)Cl.O.CC1(C)N([O])C(C)(C)CCC1>[O:50]=[C:49]([CH2:48][CH2:47][C:41]1[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=1)/[CH:51]=[CH:25]/[C@@H:8]1[C@@H:3]2[C@@H:2]([O:7][C:5](=[O:6])[CH2:4]2)[CH2:1][C@H:9]1[O:10][C:11](=[O:12])[C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:15][CH:14]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

12

Reactant 8

HCID 311Citric AcidHCID 3776IsopropanolHCID 14798Sodium HydroxideHCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 2724295(1,1'-Biphenyl)-4-carboxylic acid, (3aR,4S,5R,6aS)-hexahydro-4-(hydroxymethyl)-2-oxo-2H-cyclopenta(b)furan-5-yl ester
HCID 2733973
Dimethyl(2-oxo-4-phenylbutyl)phosphonate
HCID 23665760Sodium Hypochlorite

Product 1

HCID 10005375(1S,5R,6R,7R)-6-(3-oxo-5-phenyl-1E-pentenyl)-7-((4-phenylbenzoyl)oxy)-2-oxabicyclo(3.3.0)octan-3-oneYield 84%

Reagents, catalysts & solvents 3

HCID 2724126TempoCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of (−)-Corey lactone 5-(4-phenylbenzoate) (17.6 g, 50.0 mmol) and TEMPO (0.16 g, 1.0 mmol) in CH2Cl2 (100 mL) was added to a solution of NaBr (0.5 g, 5.0 mmol), NaHCO3 (12.6 g, 150.0 mmol) and IPA (6.0 g, 100.0 mmol) in water (100 mL). 5% aq. NaOCl (about 150 mL) was added dropwise to the stirred mixture at −5 to 0° C. until disappearance of Corey lactone (TLC monitoring). The obtained mixture was stirred for 0.5 h at the same temperature. The aqueous layer was separated and extracted with CH2Cl2 (50 mL). The combined organic layers was added dropwise over 1 h to a stirred mixture of a solution of PhCH2CH2COCH2PO(OMe)2 (15.4 g, 60.0 mmol) in CH2Cl2 (20 mL) and 30% NaOH (8.0 g, 60.0 mmol) at 0–5° C. The mixture was stirred 0.5 h at the same temperature and treated with 10% aq. citric acid (100 mL). The aqueous layer was separated and extracted with CH2Cl2 (50 mL). The combined organic layers were dried over Na2SO4, filtered through short silica gel column and concentrated in vacuo. The oily residue (24.2 g) was dissolved in refluxed EtOH (150 mL) and cooled in ice bath. The precipitate was filtered off, washed with cold EtOH and dried in vacuo to give 20.1 g (84%) of (3aR,4R,5R,6aS)-4-(3-oxo-5-phenyl-1E-pentenyl)-5-(4-phenylbenzoyloxy)-hexahydro-2H-cyclopenta[b]furan-2-one with 99.4% purity by HPLC: mp 129–130° C., [α]20D −142° (c 1.0, CHCl3); 1H NMR spectrum confirms the structure.

Workup

  1. customThe aqueous layer was separated
  2. extractionextracted with CH2Cl2 (50 mL)
  3. stirringThe mixture was stirred 0.5 h at the same temperature
  4. customThe aqueous layer was separated
  5. extractionextracted with CH2Cl2 (50 mL)
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. filtrationfiltered through short silica gel column
  8. concentrationconcentrated in vacuo
  9. dissolutionThe oily residue (24.2 g) was dissolved in refluxed EtOH (150 mL)
  10. temperaturecooled in ice bath
  11. filtrationThe precipitate was filtered off
  12. washwashed with cold EtOH
  13. customdried in vacuo

Sources & evidence

ORD record
ord-2b182edc646e45afa2e50962511a62cf
Source dataset
uspto-grants-2007_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07166730B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes