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

HRID 218261Notes

Reaction equation

HRID 218261 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+].[CH2:21]([O:23][C:24]1[CH:31]=[CH:30][C:27]([CH:28]=O)=[C:26]([O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[C:25]=1[O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:43])[CH3:42])[CH3:22].O>C1COCC1>[Si:33]([O:32][C:26]1[C:27](/[CH:28]=[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:30][CH:31]=[C:24]([O:23][CH2:21][CH3:22])[C:25]=1[O:40][Si:41]([C:44]([CH3:45])([CH3:47])[CH3:46])([CH3:42])[CH3:43])([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34]

Participants

6

Reactant 4

HCID 962WaterHCID 233739753,4,5-Trimethoxybenzylphosphonium bromideHCID 859964854-Ethoxy-2,3-di(t-butyldimethylsilyloxy)benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 601306911,2-Di(t-butyldimethylsilyloxy)-3-ethoxy-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-benzeneYield 34%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

n-Butyl lithium (0.85 mL, 1.36 mmol, 1.6 M in hexanes) was added dropwise over 10 min to a solution of 3,4,5-trimethoxybenzylphosphonium bromide (0.58 g, 1.12 mmol) in THF (7 mL) at −10° C. The reaction mixture was stirred at this temperature for 15 min then cooled to −70 C and a solution of 35 (0.47 g, 1.14 mmol) in THF (3 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 (0.67 g). Purification by column chromatography (SiO2 2:98 EtOAc:cyclohexane+1% Et3N) gave 36 (0.21 g, 34%) as an 89:11 mixture of Z:E isomers.

Workup

  1. temperaturethen cooled to −70 C
  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 (0.67 g)
  9. customPurification by column chromatography (SiO2 2:98 EtOAc:cyclohexane+1% Et3N)

Sources & evidence

ORD record
ord-bc7cbebff0c643d29402b9c53bd0a05c
Source dataset
uspto-grants-2012_06
Patent number
US08198302B2

Reaction notes

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