Ammonium Chloride → 3,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-[5-(4-ethylphenyl)methyl-2-(2-trityloxyethyl)thiophen-3-yl]-tetrahydropyran-2-ol

HRID 499731Notes

Reaction equation

HRID 499731 reaction equation
Br[C:2]1[CH:6]=[C:5]([CH2:7][C:8]2[CH:13]=[CH:12][C:11]([CH2:14][CH3:15])=[CH:10][CH:9]=2)[S:4][C:3]=1[CH2:16][CH2:17][O:18][C:19]([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.C([Li])CCC.[CH2:43]([O:50][CH:51]1[CH:56]([O:57][CH2:58][C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)[CH:55]([O:65][CH2:66][C:67]2[CH:72]=[CH:71][CH:70]=[CH:69][CH:68]=2)[CH:54]([CH2:73][O:74][CH2:75][C:76]2[CH:81]=[CH:80][CH:79]=[CH:78][CH:77]=2)[O:53][C:52]1=[O:82])[C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1.[Cl-].[NH4+]>C1COCC1.CCCCCC>[CH2:43]([O:50][CH:51]1[CH:56]([O:57][CH2:58][C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)[CH:55]([O:65][CH2:66][C:67]2[CH:68]=[CH:69][CH:70]=[CH:71][CH:72]=2)[CH:54]([CH2:73][O:74][CH2:75][C:76]2[CH:77]=[CH:78][CH:79]=[CH:80][CH:81]=2)[O:53][C:52]1([C:2]1[CH:6]=[C:5]([CH2:7][C:8]2[CH:13]=[CH:12][C:11]([CH2:14][CH3:15])=[CH:10][CH:9]=2)[S:4][C:3]=1[CH2:16][CH2:17][O:18][C:19]([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[OH:82])[C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 45855083,4,5-Tribenzyloxy-6-(benzyloxymethyl)tetrahydropyran-2-oneHCID 684604163-Bromo-5-((4-ethylphenyl)methyl)-2-(2-trityloxyethyl)thiopheneHCID 178418339Butyllithium

Product 1

HCID 866266373,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-[5-(4-ethylphenyl)methyl-2-(2-trityloxyethyl)thiophen-3-yl]-tetrahydropyran-2-olYield 65%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

Under a nitrogen stream, to a solution of 3-bromo-5-((4-ethylphenyl)methyl)-2-(2-trityloxyethyl)thiophene (1.45 g, 2.55 mmol) in anhydrous THF (40 ml), a hexane solution of n-butyllithium (1.6 M, 1.76 ml, 2.81 mmol) was added dropwise at −78° C. and the mixture was stirred for 15 minutes. To this solution was added a solution of 3,4,5-trisbenzyloxy-6-(benzyloxymethyl)tetrahydropyran-2-one (1.50 g, 2.81 mmol) in anhydrous THF (10 ml) dropwise at −78° C. and the resulting solution was stirred at the same temperature for 10 minutes. After addition of saturated aqueous ammonium chloride, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and then evaporated under reduced pressure to remove the solvent. The resulting residue was purified by silica gel column chromatography (developing solution=ethyl acetate:n-hexane (1:20)) to give the titled compound (1.70 g, 65%).

Workup

  1. stirringthe resulting solution was stirred at the same temperature for 10 minutes
  2. extractionthe reaction mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customevaporated under reduced pressure
  6. customto remove the solvent
  7. customThe resulting residue was purified by silica gel column chromatography (developing solution=ethyl acetate:n-hexane (1:20))

Sources & evidence

ORD record
ord-be7255b86c9e47069d6c76538c2b9a07
Source dataset
uspto-grants-2010_08
Patent number
US07767651B2

Reaction notes

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