Sodium hydride → HCID 86728589, compound

HRID 1410303Notes

Reaction equation

HRID 1410303 reaction equation
[CH2:1]([O:4][C:5]1[CH:10]=[C:9]([Cl:11])[C:8]([CH2:12][C:13]2[CH:18]=[CH:17][C:16]([O:19][CH2:20][CH3:21])=[CH:15][CH:14]=2)=[CH:7][C:6]=1[C@@H:22]1[O:27][C@H:26]([CH2:28][OH:29])[C@@H:25]([O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C@H:24]([O:38][CH2:39][C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[C@H:23]1[O:46][CH2:47][C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1)[CH:2]=[CH2:3].[H-].[Na+].Br[CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][O:62][Si:63]([C:76]([CH3:79])([CH3:78])[CH3:77])([C:70]1[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=1)[C:64]1[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=1>CN(C)C=O>[CH2:1]([O:4][C:5]1[CH:10]=[C:9]([Cl:11])[C:8]([CH2:12][C:13]2[CH:14]=[CH:15][C:16]([O:19][CH2:20][CH3:21])=[CH:17][CH:18]=2)=[CH:7][C:6]=1[C@@H:22]1[O:27][C@H:26]([CH2:28][O:29][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][O:62][Si:63]([C:76]([CH3:77])([CH3:79])[CH3:78])([C:70]2[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=2)[C:64]2[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=2)[C@@H:25]([O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C@H:24]([O:38][CH2:39][C:40]2[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=2)[C@H:23]1[O:46][CH2:47][C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1)[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 10408998Silane, [(5-bromopentyl)oxy](1,1-dimethylethyl)diphenyl-HCID 86728587HCID 86728587, compound

Product 1

HCID 86728589HCID 86728589, compoundYield 42%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of ((2R,3R,4R,5S,6S)-6-(2-(allyloxy)-4-chloro-5-(4-ethoxybenzyl)phenyl)-3,4,5-tris(benzyloxy)tetrahydro-2H-pyran-2-yl)methanol (16, 1.1 g, 1.51 mmol) in N,N-dimethylformamide (25 mL) was added sodium hydride (60% dispersion in mineral oil, 120.4 mg, 3.01 mmol) at 0° C., and the reaction mixture was stirred at ambient temperature for 0.5 h. After 1 h at room temperature, the reaction mixture was re-cooled to 0° C. and (5-Bromopentyloxy)(tert-butyl)diphenylsilane (27, 980 mg, 2.42 mmol) was added dropwise, and the mixture was stirred with gradual warming to ambient temperature over 5 h. After re-cooling to 0° C., the reaction mixture was quenched by addition of water (25 mL). The mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, filtered and evaporated in vacuo. The resulting crude residue was purified on a Biotage® purification apparatus (silica gel, 5 to 20% tetrahydrofuran in hexanes gradient) to yield the title compound (28, 664 mg, 0.63 mmol, 42%) as yellowish oil.

Workup

  1. waitAfter 1 h at room temperature
  2. temperaturethe reaction mixture was re-cooled to 0° C.
  3. stirringthe mixture was stirred
  4. temperaturewith gradual warming to ambient temperature over 5 h
  5. temperatureAfter re-cooling to 0° C.
  6. customthe reaction mixture was quenched by addition of water (25 mL)
  7. additionThe mixture was diluted with water
  8. extractionextracted with ethyl acetate
  9. washThe organic layer was washed with brine
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. customevaporated in vacuo
  13. customThe resulting crude residue was purified on a Biotage® purification apparatus (silica gel, 5 to 20% tetrahydrofuran in hexanes gradient)

Sources & evidence

ORD record
ord-3cb5c02bf1904f3ba1fc0755ee4efac3
Source dataset
uspto-grants-2014_12
Patent number
US08921412B2

Reaction notes

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