Water → 1,2,3-Tri(t-butyldimethylsilyloxy)-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-benzene

HRID 218258Notes

Reaction equation

HRID 218258 reaction equation
C([Li])CCC.[Br-].[CH3:7][O:8][C:9]1[CH:10]=[C:11]([CH:14]=[C:15]([O:19][CH3:20])[C:16]=1[O:17][CH3:18])[CH2:12][PH3+].[Si:21]([O:28][C:29]1[C:36]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])=[C:35]([O:45][Si:46]([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:48])[CH3:47])[CH:34]=[CH:33][C:30]=1[CH:31]=O)([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22].O>C1COCC1>[Si:21]([O:28][C:29]1[C:30](/[CH:31]=[CH:12]\[C:11]2[CH:10]=[C:9]([O:8][CH3:7])[C:16]([O:17][CH3:18])=[C:15]([O:19][CH3:20])[CH:14]=2)=[CH:33][CH:34]=[C:35]([O:45][Si:46]([C:49]([CH3:50])([CH3:52])[CH3:51])([CH3:48])[CH3:47])[C:36]=1[O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:39])[CH3:40])([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22]

Participants

6

Reactant 4

HCID 962WaterHCID 233739753,4,5-Trimethoxybenzylphosphonium bromideHCID 859964842,3,4-Tri(t-butyldimethylsilyloxy)benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 601306851,2,3-Tri(t-butyldimethylsilyloxy)-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-benzene

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

n-Butyl lithium (0.89 mL, 2.23 mmol, 2.5 M in hexanes) was added dropwise over 10 min to a solution of 3,4,5-trimethoxybenzylphosphonium bromide (0.96 g, 1.83 mmol) in THF (10 mL) at −10° C. The reaction mixture was stirred at this temperature for 15 min then cooled to −70° C. and a solution of 31 (0.93 g, 1.88 mmol) in THF (4 mL) was added and the reaction mixture was allowed to warm to room temperature with stirring overnight. The reaction mixture was cooled to 0° C. and water was added. The reaction mixture was extracted with TBME (3×) and the organic phase was washed successively with water and brine, dried (Na2SO4) and concentrated in vacuo to give crude product (1.5 g). Purification by column chromatography (SiO2; 5:95 TBME:cyclohexane+1% Et3N) gave 32 compound (0.6 g, 50%) as a 86:14 mixture of Z:E isomers:

Workup

  1. temperatureto warm to room temperature
  2. stirringwith stirring overnight
  3. temperatureThe reaction mixture was cooled to 0° C.
  4. extractionThe reaction mixture was extracted with TBME (3×)
  5. washthe organic phase was washed successively with water and brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customto give crude product (1.5 g)
  9. customPurification by column chromatography (SiO2; 5:95 TBME:cyclohexane+1% Et3N)

Sources & evidence

ORD record
ord-3a768ff6cd5f49368e972ada43b87e03
Source dataset
uspto-grants-2012_06
Patent number
US08198302B2

Reaction notes

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