Hydrogen Peroxide → 3-{[Tert-butyl(dimethyl)silyl]oxy}-2-[(4-iodophenoxy)methyl]-1-propanol

HRID 2066672Notes

Reaction equation

HRID 2066672 reaction equation
II.[C:3]([Si:7]([O:10][CH2:11][C:12]([CH2:14][O:15][C:16]1[CH:21]=[CH:20][C:19]([I:22])=[CH:18][CH:17]=1)=[CH2:13])([CH3:9])[CH3:8])([CH3:6])([CH3:5])[CH3:4].[BH4-].[Na+].[OH:25]O.[OH-].[Na+]>C1COCC1.O>[Si:7]([O:10][CH2:11][CH:12]([CH2:14][O:15][C:16]1[CH:21]=[CH:20][C:19]([I:22])=[CH:18][CH:17]=1)[CH2:13][OH:25])([C:3]([CH3:6])([CH3:4])[CH3:5])([CH3:9])[CH3:8]

Participants

8

Reactant 5

HCID 784Hydrogen PeroxideHCID 807IodineHCID 14798Sodium HydroxideHCID 4311764Sodium borohydrideHCID 66956533HCID 66956533, compound

Product 1

HCID 669567553-{[Tert-butyl(dimethyl)silyl]oxy}-2-[(4-iodophenoxy)methyl]-1-propanolYield 71%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of iodine (282 mg, 1.11 mmol) in anhydrous THF (1.5 mL, then 2×0.75 mL to rinse) was added dropwise (over 40 min) to a stirred mixture of alkene 167 (1.71 g, 4.23 mmol) and powdered NaBH4 (90 mg, 2.38 mmol) in anhydrous THF (5.5 mL) at 0° C. under N2. After stirring at 0° C. for 4 h, and then at room temperature for 13 h, the mixture was again cooled to 0° C., treated with 30% H2O2 (2.4 mL) and 3N NaOH (2.4 mL), and then stirred at room temperature for 3 h. Water (50 mL) was then added, and the mixture was extracted with EtOAc (4×50 mL). The extracts were washed with brine (50 mL) and evaporated to dryness and the residue was chromatographed on silica gel. Elution with 0-2% EtOAc/petroleum ether firstly gave foreruns, and then further elution with 4-5% EtOAc/petroleum ether gave 3-{[tert-butyl(dimethyl)silyl]oxy}-2-[(4-iodophenoxy)methyl]-1-propanol (169) (1.26 g, 71%) as a pale yellow oil; 1H NMR (CDCl3) δ 7.55 (dt, J=9.0, 2.7 Hz, 2H), 6.69 (dt, J=9.0, 2.7 Hz, 2H), 4.06 (dd, J=9.3, 6.7 Hz, 1H), 4.01 (dd, J=9.3, 5.9 Hz, 1H), 3.93-3.80 (m, 4H), 2.36 (dd, J=6.3, 5.1 Hz, 1H), 2.17 (sept, J=5.4 Hz, 1H), 0.89 (s, 9H), 0.06, 0.05 (2 s, 6H); HRFABMS calcd for C16H28IO3Si m/z [M+H]+ 423.0853. found 423.0849.

Workup

  1. additionwas added dropwise (over 40 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 (4×50 mL)
  6. washThe extracts were washed with brine (50 mL)
  7. customevaporated to dryness
  8. customthe residue was chromatographed on silica gel
  9. washElution with 0-2% EtOAc/petroleum ether firstly gave foreruns
  10. washfurther elution with 4-5% EtOAc/petroleum ether

Sources & evidence

ORD record
ord-01ab5e2cc20b4de0b8cfe5bc45797f16
Source dataset
uspto-grants-2012_10
Patent number
US08293734B2

Reaction notes

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