Hydrogen Peroxide → Isopropyl (Z)-7-((1R,2R,3R,5S)-2-((3R,E)-3-(tert-butyldimethylsilyloxy)-4-(3-(trifluoromethyl)-phenoxy)-but-1-enyl)-3-(tert-butyldimethylsilyloxy)-5-hydroxy-cyclopentyl)-hept-5-enoate

HRID 402867Notes

Reaction equation

HRID 402867 reaction equation
[Si:1]([O:8][C@@H:9]([CH2:38][O:39][C:40]1[CH:45]=[CH:44][CH:43]=[C:42]([C:46]([F:49])([F:48])[F:47])[CH:41]=1)/[CH:10]=[CH:11]/[C@H:12]1[C@H:16]([O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])[CH2:15][C:14](=[O:25])[C@@H:13]1[CH2:26]/[CH:27]=[CH:28]\[CH2:29][CH2:30][CH2:31][C:32]([O:34][CH:35]([CH3:37])[CH3:36])=[O:33])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].CCC(C)[BH-](C(C)CC)C(C)CC.[Li+].OO.[Na+].[Cl-]>C1COCC1>[Si:1]([O:8][C@@H:9]([CH2:38][O:39][C:40]1[CH:45]=[CH:44][CH:43]=[C:42]([C:46]([F:48])([F:47])[F:49])[CH:41]=1)/[CH:10]=[CH:11]/[C@H:12]1[C@H:16]([O:17][Si:18]([C:21]([CH3:23])([CH3:22])[CH3:24])([CH3:19])[CH3:20])[CH2:15][C@H:14]([OH:25])[C@@H:13]1[CH2:26]/[CH:27]=[CH:28]\[CH2:29][CH2:30][CH2:31][C:32]([O:34][CH:35]([CH3:37])[CH3:36])=[O:33])([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 5234Sodium ChlorideHCID 3611392Lithium tri-s-butylborohydrideHCID 57912505Isopropyl (Z)-7-((1R,2R,3R)-2-((3R,E)-3-(tert-butyldimethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)-but-1-enyl)-3-(tert-butyldimethylsilyloxy)-5-oxo-cyclopentyl)-hept-5-enoate

Product 1

HCID 67226385Isopropyl (Z)-7-((1R,2R,3R,5S)-2-((3R,E)-3-(tert-butyldimethylsilyloxy)-4-(3-(trifluoromethyl)-phenoxy)-but-1-enyl)-3-(tert-butyldimethylsilyloxy)-5-hydroxy-cyclopentyl)-hept-5-enoateYield 50%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a cold solution of crude compound (10a) (155 g) prepared in EXAMPLE 16 in THF (450 mL) was added a solution of L-Selectride in THF (1.06 M, 230 mL). 30% H2O2 (40 mL) was then added at −30° C., stirred for 1 h. Saturated aqueous NaCl (150 mL) was added into the reaction mixture, the layers were separated, the aqueous layer was extracted twice with MTBE or toluene (PhMe) (300 mL each) and then the combined organic layer was concentrated under reduced pressure. The crude product was purified by column chromatography to furnish 51.3 g of compound (11a) (92% HPLC purity, 50% yield). This was used directly in EXAMPLE 18.

Workup

  1. customthe layers were separated
  2. extractionthe aqueous layer was extracted twice with MTBE or toluene (PhMe) (300 mL each)
  3. concentrationthe combined organic layer was concentrated under reduced pressure
  4. customThe crude product was purified by column chromatography

Sources & evidence

ORD record
ord-72090d89795742c8961914d42656415c
Source dataset
uspto-grants-2014_06
Patent number
US08742143B2

Reaction notes

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