Tetrahydrofuran → Tert-butyl[5-{[tert-butyl(dimethyl)silyl]oxy}-2-(4-methylenecyclohexyl)phenoxy]dimethylsilane

HRID 1007966Notes

Reaction equation

HRID 1007966 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].[Si:7]([O:14][C:15]1[CH:20]=[C:19]([O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23])[CH:18]=[CH:17][C:16]=1C1CCC(=O)CC1)([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8].O1C[CH2:39][CH2:38][CH2:37]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:10]([Si:7]([O:14][C:15]1[CH:20]=[C:19]([O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23])[CH:18]=[CH:17][C:16]=1[CH:38]1[CH2:39][CH2:3][C:2](=[CH2:5])[CH2:1][CH2:37]1)([CH3:8])[CH3:9])([CH3:13])([CH3:12])[CH3:11]

Participants

5

Reactant 3

HCID 8028Tetrahydrofuran2×HCID 223378144-(2,4-Bis{[tert-butyl(dimethyl)silyl]oxy}phenyl)cyclohexan-1-oneHCID 23665647Potassium tert-butoxide

Product 1

HCID 17946008Tert-butyl[5-{[tert-butyl(dimethyl)silyl]oxy}-2-(4-methylenecyclohexyl)phenoxy]dimethylsilaneYield 93%

Reagents, catalysts & solvents 1

HCID 74505Methyltriphenyliphosphonium bromideCatalyst

Conditions

Temperature
0 °C

Procedure

To a round bottomed flask was added methyltriphenylphosphonium bromide (0.99 g) and tetrahydrofuran (30 ml). The resulting suspension was cooled to 0° C. and potassium tert-butoxide (0.31 g) was added in one portion. The resulting solution was stirred at 0° C. for 0.5 hr, then 4-(2,4-bis{[tert-butyl(dimethyl)silyl]oxy}phenyl)cyclohexanone (0.60 g) added as a solution in tetrahydrofuran (10 ml). The solution was stirred for 1 hr at 0° C., then allowed to warm to room temperature and stirred for 15 hr. The reaction mixture was partitioned between ethyl acetate (20 ml) and saturated ammonium chloride solution (20 ml). The layers were separated and the aqueous layer extracted with ethyl acetate (2×20 ml). The combined organic phases were washed with brine (20 ml), dried over magnesium sulfate, filtered and concentrated in vacuo. Purification via flash chromatography (SiO2, ethyl acetate/petroleum ether, 1:9 v/v) furnished the title compound (0.56 g, 93%) as a colourless oil. δH (CDCl3): 0.17 (6H, s), 0.24 (6H, s), 0.97 (9H, s), 1.03 (9H, s), 1.34-1.47 (2H, m), 1.86-1.94 (2H, m), 2.10-2.20 (2H, m), 2.35-2.43 (2H, m), 3.00 (1H, ft), 4.64 (2H, m), 6.29 (1H, d), 6.39 (1H, dd), 6.94 (1H, d).

Workup

  1. stirringThe solution was stirred for 1 hr at 0° C.
  2. temperatureto warm to room temperature
  3. stirringstirred for 15 hr
  4. customThe reaction mixture was partitioned between ethyl acetate (20 ml) and saturated ammonium chloride solution (20 ml)
  5. customThe layers were separated
  6. extractionthe aqueous layer extracted with ethyl acetate (2×20 ml)
  7. washThe combined organic phases were washed with brine (20 ml)
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customPurification via flash chromatography (SiO2, ethyl acetate/petroleum ether, 1:9 v/v)

Sources & evidence

ORD record
ord-4af03587dee74a0780efee8ec9f225f0
Source dataset
uspto-grants-2004_09
Patent number
US06797731B2

Reaction notes

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