Iodine → 4-(tert-Butyl-diphenyl-silanyloxy)-1-(4-chloro-phenyl)-butan-1-ol

HRID 1643306Notes

Reaction equation

HRID 1643306 reaction equation
II.Br[C:4]1[CH:9]=[CH:8][C:7]([Cl:10])=[CH:6][CH:5]=1.[C:11]([Si:15]([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[O:16][CH2:17][CH2:18][CH2:19][CH:20]=[O:21])([CH3:14])([CH3:13])[CH3:12]>C1COCC1>[C:11]([Si:15]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[O:16][CH2:17][CH2:18][CH2:19][CH:20]([C:4]1[CH:9]=[CH:8][C:7]([Cl:10])=[CH:6][CH:5]=1)[OH:21])([CH3:14])([CH3:12])[CH3:13]

Participants

5

Reactant 3

HCID 807IodineHCID 7806p-BromochlorobenzeneHCID 108711124-(Tert-butyldiphenylsilyloxy)butanal

Product 1

HCID 595688264-(tert-Butyl-diphenyl-silanyloxy)-1-(4-chloro-phenyl)-butan-1-olYield 49.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
63 °C

Procedure

To a suspension of Mg turnings (145 mg, 6.0 mg-at.) and catalytic amount of iodine in 20 mL THF was added dropwise 1-Bromo-4-chloro-benzene (382 mg, 2.0 mmol) with heating over a period of 30 min. After stirring for an additional 30 min at 63° C. the mixture was cooled to −30° C. and 4-(tert-Butyl-diphenyl-silanyloxy)-butyraldehyde (500 mg, 1.53 mmol) was added slowly as a solution in 5 mL THF. The temperature was maintained at −30° C. for 1 h and slowly raised to room temperature. The excess Grignard reagent was destroyed by careful addition of saturated aqueous NH4Cl (20 mL). The mixture was extracted with ethyl acetate (3×30 mL) and the combined organic layers washed with brine (2×20 mL). After removal of the solvent under reduced pressure the product was isolated by flash column chromatography eluting with 0 to 50% EtOAc/hexanes to afford 330 mg of the title compound as a light yellow oil.

Workup

  1. temperaturewith heating over a period of 30 min
  2. temperaturewas cooled to −30° C.
  3. temperatureThe temperature was maintained at −30° C. for 1 h
  4. temperatureslowly raised to room temperature
  5. customThe excess Grignard reagent was destroyed by careful addition of saturated aqueous NH4Cl (20 mL)
  6. extractionThe mixture was extracted with ethyl acetate (3×30 mL)
  7. washthe combined organic layers washed with brine (2×20 mL)
  8. customAfter removal of the solvent under reduced pressure the product
  9. customwas isolated by flash column chromatography
  10. washeluting with 0 to 50% EtOAc/hexanes

Sources & evidence

ORD record
ord-db984b80c9254d60b4de04632e1450e9
Source dataset
uspto-grants-2012_02
Patent number
US08119692B2

Reaction notes

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