Hydrogen Peroxide → HCID 59315611, compound

HRID 1930508Notes

Reaction equation

HRID 1930508 reaction equation
CC(=CC)C.[Br:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[C@@H:13]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH2:14][CH:15]=[CH2:16].[OH-:25].[Na+].OO>O1CCCC1.C(Cl)Cl>[Br:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[C@@H:13]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH2:14][CH2:15][CH2:16][OH:25]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 105532-Methyl-2-buteneHCID 14798Sodium HydroxideHCID 59315607HCID 59315607, compound2×

Product 1

HCID 59315611HCID 59315611, compoundYield 34.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 2-methyl-2-butene (204 mmol, 21.68 mL) dissolved in tetrahydrofuran (150 mL) was cooled in a salt-ice bath and 1M boran-THF complex (34.1 mmol, 34.1 mL) was slowly added maintaining the temperature below 0° C. Upon complete addition the reaction mixture was left to stir for 10 minutes at 0° C. and then a tetrahydrofuran solution of (S)-tert-butyl 1-(2-bromophenyl)but-3-enylcarbamate (compound 4; 68.1 mmol, 22.23 g) was added slowly maintaining the temperature below 5° C. Once the addition was complete the cooling bath was removed and the temperature allowed to warm to room temperature and left to stir for 60 minutes. After 60 minutes the reaction mixture was cooled back to 0° C. and 4N sodium hydroxide (80 mmol, 20 mL) was slowly added at below 5° C. and this was followed by 27.5% aqueous hydrogen peroxide solution (68.1 mmol, 20 mL) keeping the temperature below 5° C., once the addition was complete the cooling bath was removed and the temperature allowed to warm to ambient temperature and left to stir overnight. The reaction mixture was diluted with ether (500 mL) then water (500 mL), the aqueous was phase separated and the aqueous re-extracted with ether (3×500 mL). The combined organic layers were dried over sodium sulfate, filtered and evaporated to give an white solid that was taken up in methylene chloride an loaded on to a silica pad and eluted with 40% ethyl acetate-heptane to give (S)-tert-butyl 1-(2-bromophenyl)-4-hydroxybutylcarbamate (8.08 g), MS (ES): m/z [M+H]+ 344 and 346.

Workup

  1. temperaturewas cooled in a salt-ice bath
  2. addition1M boran-THF complex (34.1 mmol, 34.1 mL) was slowly added
  3. temperaturemaintaining the temperature below 0° C
  4. additionUpon complete addition the reaction mixture
  5. waitwas left
  6. temperaturemaintaining the temperature below 5° C
  7. additionOnce the addition
  8. customwas removed
  9. temperatureto warm to room temperature
  10. waitleft
  11. stirringto stir for 60 minutes
  12. temperatureAfter 60 minutes the reaction mixture was cooled back to 0° C.
  13. customthe temperature below 5° C.
  14. additiononce the addition
  15. customwas removed
  16. temperatureto warm to ambient temperature
  17. waitleft
  18. stirringto stir overnight
  19. additionThe reaction mixture was diluted with ether (500 mL)
  20. customseparated
  21. extractionthe aqueous re-extracted with ether (3×500 mL)
  22. dry with materialThe combined organic layers were dried over sodium sulfate
  23. filtrationfiltered
  24. customevaporated
  25. customto give an white solid that
  26. washeluted with 40% ethyl acetate-heptane

Sources & evidence

ORD record
ord-33e186293c5d40eea92f0e2cfadfaa96
Source dataset
uspto-grants-2012_05
Patent number
US08188123B2

Reaction notes

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