tert-Butyl 3-oxo-8-azabicyclo(3.2.1)octane-8-carboxylate → 3-Methylene-8-Boc-8-Azabicyclo[3.2.1]Octane

HRID 473805Notes

Reaction equation

HRID 473805 reaction equation
[CH3:1]C(C)([O-])C.[K+].O=[C:8]1[CH2:14][CH:13]2[N:15]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH:10]([CH2:11][CH2:12]2)[CH2:9]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1.CCCCCC>[CH2:1]=[C:8]1[CH2:14][CH:13]2[N:15]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH:10]([CH2:11][CH2:12]2)[CH2:9]1

Participants

6

Reactant 2

HCID 2794767tert-Butyl 3-oxo-8-azabicyclo(3.2.1)octane-8-carboxylateHCID 23665647Potassium tert-butoxide

Product 1

HCID 575354833-Methylene-8-Boc-8-Azabicyclo[3.2.1]OctaneYield 91.6%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

Potassium tert-butoxide (0.62 g, 5.5 mmol) was added to a suspension of methyltriphenylphosphonium bromide (1.98 g, 5.5 mmol) in tetrahydrofuran (20 mL) and the resulting mixture was stirred at room temperature for one hour. A solution of tert-butyl 3-oxo-8-azabicyclo[3.2.1]octane-8-carboxylate (0.50 g, 2.2 mmol) in tetrahydrofuran (5 mL) was then added and the resulting mixture was stirred at 35° C. for two hours. The mixture was cooled, diluted with hexane (100 mL), filtered, and the filtrate was washed with water then brine, dried over sodium sulfate, filtered and concentrated. The residue was purified by silica gel chromatography (20% ethyl acetate in hexanes) to give tert-butyl 3-methylene-8-azabicyclo[3.2.1]octane-8-carboxylate (0.45 g, 91% yield). GC-MS (EI) for C13H21NO2: 223 (M+).

Workup

  1. stirringthe resulting mixture was stirred at 35° C. for two hours
  2. temperatureThe mixture was cooled
  3. filtrationfiltered
  4. washthe filtrate was washed with water
  5. dry with materialbrine, dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by silica gel chromatography (20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-5cdefcca26de42d9a36889a37df6969a
Source dataset
uspto-grants-2014_01
Patent number
US08637499B2

Reaction notes

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