Hydrogen Peroxide → HCID 66956821, compound

HRID 2066668Notes

Reaction equation

HRID 2066668 reaction equation
II.[C:3]([Si:7]([CH3:26])([CH3:25])[O:8][CH2:9][C:10]([CH2:12][O:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][C:21]([F:24])([F:23])[F:22])=[CH:16][CH:15]=1)=[CH2:11])([CH3:6])([CH3:5])[CH3:4].[BH4-].[Na+].[OH:29]O.[OH-].[Na+]>C1COCC1.O>[Si:7]([O:8][CH2:9][CH:10]([CH2:12][O:13][C:14]1[CH:15]=[CH:16][C:17]([O:20][C:21]([F:24])([F:22])[F:23])=[CH:18][CH:19]=1)[CH2:11][OH:29])([C:3]([CH3:4])([CH3:6])[CH3:5])([CH3:25])[CH3:26]

Participants

8

Reactant 5

HCID 784Hydrogen PeroxideHCID 807IodineHCID 14798Sodium HydroxideHCID 4311764Sodium borohydrideHCID 66955670Tert-butyl(dimethyl)[(2-{[4-(trifluoromethoxy)phenoxy]methyl}-2-propenyl)oxy]silane

Product 1

HCID 66956821HCID 66956821, compoundYield 61%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of iodine (825 mg, 3.25 mmol) in anhydrous THF (5 mL, then 2×3 mL to rinse) was added dropwise (over 70 min) to a stirred mixture of alkene 166 (5.21 g, 14.4 mmol) and powdered NaBH4 (257 mg, 6.79 mmol) in anhydrous THF (18 mL) at 0° C. under N2. After stirring at 0° C. for 3 h, and then at room temperature for 13 h, the mixture was again cooled to 0° C., treated with 30% H2O2 (6.8 mL) and 3N NaOH (6.8 mL), and then stirred at room temperature for 3 h. Water (160 mL) was then added, and the mixture was extracted with EtOAc (4×160 mL). The extracts were washed with brine (80 mL) and evaporated to dryness and the residue was chromatographed on silica gel. Elution with 0-3.5% EtOAc/petroleum ether firstly gave foreruns, and then further elution with 4-8% EtOAc/petroleum ether gave 3-{[tert-butyl(dimethyl)silyl]oxy}-2-{[4-(trifluoromethoxy)phenoxy]methyl}-1-propanol (168) (3.32 g, 61%) as a colourless oil; 1H NMR (CDCl3) δ 7.13 (br d, J=9.0 Hz, 2H), 6.89 (dt, J=9.1, 3.0 Hz, 2H), 4.08 (dd, J=9.3, 6.6 Hz, 1H), 4.04 (dd, J=9.3, 6.0 Hz, 1H), 3.94-3.81 (m, 4H), 2.36 (dd, J=6.1, 5.2 Hz, 1H), 2.19 (m, 1H), 0.89 (s, 9H), 0.07, 0.05 (2 s, 6H); HRFABMS calcd for C17H28F3O4Si m/z [M+H]+ 381.1709. found 381.1707.

Workup

  1. additionwas added dropwise (over 70 min)
  2. waitat room temperature for 13 h
  3. temperaturethe mixture was again cooled to 0° C.
  4. stirringstirred at room temperature for 3 h
  5. extractionthe mixture was extracted with EtOAc (4×160 mL)
  6. washThe extracts were washed with brine (80 mL)
  7. customevaporated to dryness
  8. customthe residue was chromatographed on silica gel
  9. washElution with 0-3.5% EtOAc/petroleum ether firstly gave foreruns
  10. washfurther elution with 4-8% EtOAc/petroleum ether

Sources & evidence

ORD record
ord-39662b803c1b4b22b1e5e772c4700382
Source dataset
uspto-grants-2012_10
Patent number
US08293734B2

Reaction notes

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