Hydrogen Peroxide → [4-((1r,2s,3r,5s)-3-(Tert-butyl-dimethyl-silanyloxy)-2-{4-[(tert-butyl-dimethyl-silanyloxy)-cyclohexyl-methyl]-phenyl}-5-hydroxy-cyclopentyl)-but-2-ynyloxy]-acetic acid methyl ester

HRID 9239

Reaction equation

HRID 9239 reaction equation
CCC(C)[BH-](C(C)CC)C(C)CC.[Li+].[CH3:15][O:16][C:17](=[O:59])[CH2:18][O:19][CH2:20][C:21]#[C:22][CH2:23][C@H:24]1[C:28](=[O:29])[CH2:27][C@@H:26]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[C@@H:25]1[C:38]1[CH:43]=[CH:42][C:41]([CH:44]([O:51][Si:52]([C:55]([CH3:58])([CH3:57])[CH3:56])([CH3:54])[CH3:53])[CH:45]2[CH2:50][CH2:49][CH2:48][CH2:47][CH2:46]2)=[CH:40][CH:39]=1.OO.[NH4+].[Cl-]>C1COCC1>[CH3:15][O:16][C:17](=[O:59])[CH2:18][O:19][CH2:20][C:21]#[C:22][CH2:23][C@H:24]1[C@@H:28]([OH:29])[CH2:27][C@@H:26]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[C@@H:25]1[C:38]1[CH:39]=[CH:40][C:41]([CH:44]([O:51][Si:52]([C:55]([CH3:58])([CH3:57])[CH3:56])([CH3:54])[CH3:53])[CH:45]2[CH2:46][CH2:47][CH2:48][CH2:49][CH2:50]2)=[CH:42][CH:43]=1

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 25517Ammonium ChlorideHCID 3611392Lithium tri-s-butylborohydrideHCID 91117818[4-((1r,2s,3r)-3-(Tert-butyl-dimethyl-silanyloxy)-2-{4-[(tert-butyl-dimethyl-silanyloxy)-cyclohexyl-methyl]-phenyl}-5-oxo-cyclopentyl)-but-2-ynyloxy]-acetic acid methyl ester

Product 1

HCID 91604517[4-((1r,2s,3r,5s)-3-(Tert-butyl-dimethyl-silanyloxy)-2-{4-[(tert-butyl-dimethyl-silanyloxy)-cyclohexyl-methyl]-phenyl}-5-hydroxy-cyclopentyl)-but-2-ynyloxy]-acetic acid methyl esterYield 61.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

L-selectride (0.76 mL, 0.76 mmol, 1 M/THF) was added to a −78° C. THF (20 mL) solution of 10-3 (415 mg, 0.63 mmol). The reaction was stirred for 1 h and then 3% H2O2 (14 mL) was added. The resulting mixture was stirred at room temperature for 45 min. and then saturated NH4Cl solution (60 mL) was added. The resulting mixture was extracted with ethyl acetate (3×40 mL) and the combined ethyl acetate solution was washed with brine. The solution was then dried (Na2SO4), filtered and evaporated. Purification by flash chromatography on silica gel (25% ethyl acetate/hexanes) gave the title alcohol (255 mg, 0.39 mmol, 61%).

Workup

  1. stirringThe resulting mixture was stirred at room temperature for 45 min.
  2. extractionThe resulting mixture was extracted with ethyl acetate (3×40 mL)
  3. washthe combined ethyl acetate solution was washed with brine
  4. dry with materialThe solution was then dried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated
  7. customPurification by flash chromatography on silica gel (25% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-41d347d7d83e44799ee2817ae32e4c2a
Source dataset
uspto-grants-2006_08
Patent number
US07091231B2

Linked notes

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