Water → HCID 54070449, compound

HRID 612337Notes

Reaction equation

HRID 612337 reaction equation
CC(C)([O-])C.[K+].[Br-].[F:8][C:9]1[CH:10]=[C:11]([CH:32]=[CH:33][C:34]=1[O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[CH2:12][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH2:43]([Si:48]1([CH3:62])[CH2:53][CH2:52][CH:51]([CH:54]2[CH2:59][CH2:58][CH:57]([CH:60]=O)[CH2:56][CH2:55]2)[CH2:50][CH2:49]1)[CH2:44][CH2:45][CH2:46][CH3:47].O>C1COCC1.C(OCC)(=O)C>[F:8][C:9]1[CH:10]=[C:11]([CH:12]=[CH:60][CH:57]2[CH2:56][CH2:55][CH:54]([CH:51]3[CH2:52][CH2:53][Si:48]([CH2:43][CH2:44][CH2:45][CH2:46][CH3:47])([CH3:62])[CH2:49][CH2:50]3)[CH2:59][CH2:58]2)[CH:32]=[CH:33][C:34]=1[O:35][Si:36]([C:39]([CH3:40])([CH3:41])[CH3:42])([CH3:37])[CH3:38]

Participants

7

Reactant 4

HCID 962WaterHCID 23665647Potassium tert-butoxideHCID 54490730HCID 54490730, compoundHCID 86754960HCID 86754960, compound

Product 1

HCID 54070449HCID 54070449, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

12.0 g of potassium t-butoxide was added to a mixture of 60 g of 3-fluoro-4-(t-butyldimethylsiloxy)benzyltriphenylphosphonium bromide and 200 ml of THF to prepare an orange-colored ylide solution. A solution, in 50 ml of THF, of 33 g of 4-(4-n-pentyl-4-methyl-4-silacyclohexyl)cyclohexane carbaldehyde was added to the ylide solution. The reaction mixture was agitated at room temperature for 2 hours, followed by pouring into iced water and extraction with ethyl acetate. After ordinary washing, drying and concentration, n-hexane was added to the resultant residue. The resulting crystals of triphenylphosphine oxide was removed by filtration and the filtrate was concentrated. The resultant reside was purified through silica gel chromatography to obtain 4-(4-(2-(3-fluoro-4-(t-butyldimethylsiloxy)phenyl)ethenyl)cyclohexyl)-1-pentyl-1-methyl-1-silacyclohexane. This product was dissolved in 200 ml of ethyl acetate and hydrogenated in the presence of a catalyst composed of 200 mg of platinum oxide at a pressure of 0.1 MPa. After theoretical consumption of hydrogen, the catalyst was removed by filtration and the resultant filtrate was concentrated. 100 ml of a THF solution of 1 mol/liter of tetrabutylammonium fluoride was added to the concentrate, followed by agitation at room temperature for 3 hours. The reaction mixture was poured into 10% hydrochloric acid. After ordinary washing, drying and concentration, the resultant residue was purified through silica gel chromatography. The purified product was reacted with 24 g of sodium hydride in 1,3-dimethyl-2-imidazolidinone to obtain a sodium salt. After ordinary washing, drying and concentration, the sodium salt was purified through silica gel chromatography, followed by recrystallization to obtain 15.0 g of the intended trans isomer.

Workup

  1. customto prepare an orange-colored ylide solution
  2. customAfter ordinary washing, drying
  3. concentrationconcentration, n-hexane
  4. additionwas added to the resultant residue
  5. customThe resulting crystals of triphenylphosphine oxide was removed by filtration
  6. concentrationthe filtrate was concentrated
  7. customThe resultant reside was purified through silica gel chromatography

Sources & evidence

ORD record
ord-7cd663a795214c7a872338949625f62a
Source dataset
uspto-grants-1999_12
Patent number
US06004478

Reaction notes

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