Ammonium Chloride → (3-{(1R,2S,3R)-3-(tert-Butyldimethylsilanyloxy)-2-[(S)-(E)-3-(tert-butyldimethylsilanoxy)oct-1-enyl]-5-oxocyclopentylsulfanyl} propylsulfanyl)acetic acid methyl ester

HRID 1862488Notes

Reaction equation

HRID 1862488 reaction equation
C([Li])(C)(C)C.[C:6]([Si:10]([O:13][C@H:14](/[CH:20]=[CH:21]/I)[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])([CH3:12])[CH3:11])([CH3:9])([CH3:8])[CH3:7].[CH3:23][O:24][C:25](=[O:46])[CH2:26][S:27][CH2:28][CH2:29][CH2:30][S:31][C:32]1[C:36](=[O:37])[CH2:35][C@@H:34]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40])[CH:33]=1.[NH4+].[Cl-]>CCCCC.CCOCC.C1COCC1>[CH3:23][O:24][C:25](=[O:46])[CH2:26][S:27][CH2:28][CH2:29][CH2:30][S:31][C@H:32]1[C:36](=[O:37])[CH2:35][C@@H:34]([O:38][Si:39]([C:42]([CH3:43])([CH3:45])[CH3:44])([CH3:41])[CH3:40])[C@@H:33]1/[CH:21]=[CH:20]/[C@@H:14]([O:13][Si:10]([C:6]([CH3:7])([CH3:9])[CH3:8])([CH3:11])[CH3:12])[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 11111369(3S)-1-Iodo-3-(tert-butyldimethylsilyloxy)-1-octeneHCID 15406175[3-[(R)-3-(tert-Butyldimethylsilanyloxy)-5-oxocyclopent-1-enylsulfanyl]propylsulfanyl}acetic acid methyl esterHCID 178418306HCID 178418306, compound

Product 1

HCID 12990739(3-{(1R,2S,3R)-3-(tert-Butyldimethylsilanyloxy)-2-[(S)-(E)-3-(tert-butyldimethylsilanoxy)oct-1-enyl]-5-oxocyclopentylsulfanyl} propylsulfanyl)acetic acid methyl esterYield 39%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolvent2×HCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

tert-Butyllithium (1.47 mL of a 1.7M solution in pentane, 2.5 mmol) was added dropwise to a solution of tert-butyl[(S)-1-((E)-2-iodovinyl) hexyloxy]dimethylsilane 6 (462.5 mg, 1.25 mmol) in Et2O (6.0 mL) at −78° C. After stirring for 30 min lithium 2-thienylcyanocuprate (6.0 mL of a 0.25M solution in THF, 1.5 mmol) was added and the reaction was stirred an additional 30 min at −78° C. A solution of enone 5 (430 mg, 1.1 mmol) in Et2O (1 mL) was added and stirring was continued for an additional 1 h. The reaction mixture was then quickly poured into saturated aqueous NH4Cl cooled to 0° C. The mixture was extracted with EtOAc and the organic portion was washed with brine, dried (Na2SO4), filtered and concentrated in vacuo. The residue was quickly purified by flash column chromatography (silica gel, 100% hexane followed by 8:1 hex/EtOAc) to afford 270 mg (39%) of the above titled compound.

Workup

  1. additionwas added
  2. stirringstirring
  3. waitwas continued for an additional 1 h
  4. temperaturecooled to 0° C
  5. extractionThe mixture was extracted with EtOAc
  6. washthe organic portion was washed with brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe residue was quickly purified by flash column chromatography (silica gel, 100% hexane followed by 8:1 hex/EtOAc)

Sources & evidence

ORD record
ord-86a5dcb7947f493c9a44587e4c28435f
Source dataset
uspto-grants-2003_03
Patent number
US06538018B1

Reaction notes

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