(1 S,2R,3R,4R)-2-allyl-4-(tert-butyldimethylsilyloxy)-3-((R,E)-3-(triethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)but-1-enyl)cyclopentyl hex-5-enoate → (8aR,9R,10R,11 aS,Z)-10-(tert-butyldimethylsilyloxy)-9-((R,E)-3-(triethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)but-1-enyl)-4,5,8,8a,9,10,11,11a-octahydrocyclopenta[b]oxecin-2(3H)-one

HRID 517382Notes

Reaction equation

HRID 517382 reaction equation
[C:1]([O:8][C@H:9]1[CH2:13][C@@H:12]([O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])[C@H:11](/[CH:22]=[CH:23]/[C@@H:24]([O:37][Si:38]([CH2:43][CH3:44])([CH2:41][CH3:42])[CH2:39][CH3:40])[CH2:25][O:26][C:27]2[CH:32]=[CH:31][CH:30]=[C:29]([C:33]([F:36])([F:35])[F:34])[CH:28]=2)[C@H:10]1[CH2:45][CH:46]=C)(=[O:7])[CH2:2][CH2:3][CH2:4][CH:5]=C>ClCCl.Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl>[Si:15]([O:14][C@@H:12]1[CH2:13][C@@H:9]2[O:8][C:1](=[O:7])[CH2:2][CH2:3][CH2:4][CH:5]=[CH:46][CH2:45][C@@H:10]2[C@H:11]1/[CH:22]=[CH:23]/[C@@H:24]([O:37][Si:38]([CH2:41][CH3:42])([CH2:39][CH3:40])[CH2:43][CH3:44])[CH2:25][O:26][C:27]1[CH:32]=[CH:31][CH:30]=[C:29]([C:33]([F:35])([F:36])[F:34])[CH:28]=1)([C:18]([CH3:19])([CH3:20])[CH3:21])([CH3:16])[CH3:17]

Participants

4

Reactant 1

HCID 131733346(1 S,2R,3R,4R)-2-allyl-4-(tert-butyldimethylsilyloxy)-3-((R,E)-3-(triethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)but-1-enyl)cyclopentyl hex-5-enoate

Product 1

HCID 131733347(8aR,9R,10R,11 aS,Z)-10-(tert-butyldimethylsilyloxy)-9-((R,E)-3-(triethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)but-1-enyl)-4,5,8,8a,9,10,11,11a-octahydrocyclopenta[b]oxecin-2(3H)-oneYield 16%

Reagents, catalysts & solvents 2

HCID 178479819HCID 178479819, compoundCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

A 50 ml two-necked round-bottom flask was flame dried and allowed to be cooled under nitrogen. (1S,2R,3R,4R)-2-allyl-4-(tert-butyldimethylsilyloxy)-3-((R,E)-3-(triethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)but-1-enyl)cyclopentyl hex-5-enoate (0.2 g, 0.29 mmol) in 4 ml of dichloromethane, and 0.02 g of Grubb's catalyst were added to the reaction flask. The reaction mixture was heated at 40° C. for 18 hours. The reaction was quenched with 0.4 ml ethylamine with stirring for 1 hour. The reaction mixture was phase separated and the aqueous layer was extracted with ethyl acetate and 4 ml saturated aqueous sodium bicarbonate solution. The organic layers were combined and dried over anhydrous magnesium sulfate. The solid was filtered off and organic solvent was evaporated off under vacuum. The crude product was purified by chromatography and then concentrated under educed pressure to provide 30 mg of the title compound (16% yield).

Workup

  1. temperatureA 50 ml two-necked round-bottom flask was flame
  2. customdried
  3. temperatureto be cooled under nitrogen
  4. customThe reaction was quenched with 0.4 ml ethylamine
  5. customseparated
  6. extractionthe aqueous layer was extracted with ethyl acetate and 4 ml saturated aqueous sodium bicarbonate solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationThe solid was filtered off
  9. customorganic solvent was evaporated off under vacuum
  10. customThe crude product was purified by chromatography
  11. concentrationconcentrated under educed pressure

Sources & evidence

ORD record
ord-5ce70d3612ba4a52b67d63d1e305bf37
Source dataset
uspto-grants-2015_08
Patent number
US09115109B2

Reaction notes

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