Benzyl Bromide → HCID 58557870, compound

HRID 1969865Notes

Reaction equation

HRID 1969865 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]12[CH2:16][CH2:15][C:12]([C:17]([O:19][CH3:20])=[O:18])([CH2:13][CH2:14]1)[CH2:11][CH2:10]2)=[O:7])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].[CH2:23](Br)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>CN(C=O)C.CCCC[N+](CCCC)(CCCC)CCCC.[I-]>[CH2:23]([N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[C:9]12[CH2:10][CH2:11][C:12]([C:17]([O:19][CH3:20])=[O:18])([CH2:15][CH2:16]1)[CH2:13][CH2:14]2)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

6

Reactant 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 58557079Methyl 4-[(tert-butoxycarbonyl)amino]bicyclo[2.2.2]octane-1-carboxylate

Product 1

HCID 58557870HCID 58557870, compoundYield 82.3%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of methyl 4-(tert-butoxycarbonylamino)bicyclo[2.2.2]octane-1-carboxylate (2.50 g, 8.82 mmol) in DMF (42 mL) at about 0° C. was added sodium hydride (60% dispersion in mineral oil, 0.706 g, 17.6 mmol). The reaction mixture was stirred for about 30 min at about 0° C. and TBAI (0.652 g, 1.76 mmol) and benzyl bromide (2.10 mL, 17.7 mmol) were added. The reaction was warmed to ambient temperature and continued to stir for about 5 h. The solvent was removed under reduced pressure and the residue was taken up in DCM (50 mL) and water (30 mL). The layers were separated and the organic phase was washed with brine (30 mL), dried over anhydrous MgSO4, filtered and concd under reduced pressure. The resulting oil was purified by silica gel chromatography eluting with a gradient of 0-30% EtOAc in heptane to give methyl 4-(benzyl(tert-butoxycarbonyl)amino)bicyclo[2.2.2]octane-1-carboxylate (2.71 g, 82%) as a clear colorless oil: LC/MS (Table 1, Method b) Rt=3.09 min; MS m/z: 374 (M+H)+.

Workup

  1. temperatureThe reaction was warmed to ambient temperature
  2. stirringto stir for about 5 h
  3. customThe solvent was removed under reduced pressure
  4. customThe layers were separated
  5. washthe organic phase was washed with brine (30 mL)
  6. dry with materialdried over anhydrous MgSO4
  7. filtrationfiltered
  8. customThe resulting oil was purified by silica gel chromatography
  9. washeluting with a gradient of 0-30% EtOAc in heptane

Sources & evidence

ORD record
ord-b5c58510a59249318e485c8816a3b096
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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