Water → 2-[3-[3-(1-Adamantyl)-4-tert.butyldimethylsilyloxyphenyl]-allyl]-1,3-dioxane

HRID 2293635Notes

Reaction equation

HRID 2293635 reaction equation
[Br-].[O:2]1[CH2:7][CH2:6][CH2:5][O:4][CH:3]1[CH2:8][CH2:9][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[C:29]12([C:39]3[C:40]([O:51][SiH:52]([CH3:54])[CH3:53])=[C:41]([CH:44]=[CH:45][C:46]=3[C:47]([CH3:50])([CH3:49])[CH3:48])[CH:42]=O)[CH2:38][CH:33]3[CH2:34][CH:35]([CH2:37][CH:31]([CH2:32]3)[CH2:30]1)[CH2:36]2.O>C1COCC1>[C:29]12([C:39]3[C:40]([O:51][SiH:52]([CH3:54])[CH3:53])=[C:41]([CH:42]=[CH:9][CH2:8][CH:3]4[O:2][CH2:7][CH2:6][CH2:5][O:4]4)[CH:44]=[CH:45][C:46]=3[C:47]([CH3:50])([CH3:48])[CH3:49])[CH2:30][CH:31]3[CH2:37][CH:35]([CH2:34][CH:33]([CH2:32]3)[CH2:38]1)[CH2:36]2

Participants

5

Reactant 3

HCID 962WaterHCID 27241682-(1,3-Dioxan-2-yl)ethyltriphenylphosphonium bromideHCID 1373291173(1-Adamantyl)-4-tert.butyl-dimethylsilyloxybenzaldehyde

Product 1

HCID 1373285792-[3-[3-(1-Adamantyl)-4-tert.butyldimethylsilyloxyphenyl]-allyl]-1,3-dioxaneYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

33 g (72.1 mmoles) of [2-(1,3-dioxan-2-yl)ethyl] triphenylphosphonium bromide are suspended in 100 ml of THF. The suspension is cooled to 0° C. and 8.5 g (75.6 mmoles) of potassium terbutylate are added in small amounts. The mixture is left to stand until its temperature reacnes 20° C. It is then stirred for 1 hour at which point it is cooled to 0° C. There is then slowly added a solution of 3-(1-adamantyl)-4-tert.butyl-dimethylsilyloxybenzaldehyde in 100 ml of TMF. Once the addition has ended, the mixture is left to stand until its temperature reacnes ambient temperature at which point it is stirred for 2 hours, then poured into water, and extracted with methylene chloride. The organic phase is decanted, washed with water, dried over MgSO4 and the solvents evaporated. The residue is purified by passage through a silica column (eluant: 50:50 mixture of CH2Cl2 and hexane), yielding 19.4 g (95% yield) of the expected mixture containing more than 90% of isomer Z, and less than 10% of isomer E.

Workup

  1. waitThe mixture is left
  2. customto stand until its temperature reacnes 20° C
  3. temperatureis cooled to 0° C
  4. additionOnce the addition
  5. waitthe mixture is left
  6. customto stand until its temperature reacnes ambient temperature at which point it
  7. stirringis stirred for 2 hours
  8. extractionextracted with methylene chloride
  9. customThe organic phase is decanted
  10. washwashed with water
  11. dry with materialdried over MgSO4
  12. customthe solvents evaporated
  13. customThe residue is purified by passage through a silica column (eluant: 50:50 mixture of CH2Cl2 and hexane)

Sources & evidence

ORD record
ord-6afcca53e8c54dda9bfa50eed112ec86
Source dataset
uspto-grants-1997_11
Patent number
US05686586

Reaction notes

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