Cesium carbonate → 2-Phenyl-2-aza-bicyclo[2.2.2]octan-3-one

HRID 2176938Notes

Reaction equation

HRID 2176938 reaction equation
[CH:1]12[CH2:8][CH2:7][CH:4]([CH2:5][CH2:6]1)[C:3](=[O:9])[NH:2]2.I[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C([O-])([O-])=O.[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O1CCOCC1>[C:11]1([N:2]2[C:3](=[O:9])[CH:4]3[CH2:7][CH2:8][CH:1]2[CH2:6][CH2:5]3)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 11575IodobenzeneHCID 1378872-Azabicyclo(2.2.2)octan-3-oneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

Product 1

HCID 539096872-Phenyl-2-aza-bicyclo[2.2.2]octan-3-oneYield 62.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
125 °C

Procedure

A mixture of 2-azabicyclo[2.2.2]octan-3-one (0.6 g, 4.8 mmol), iodo benzene (1.16 g, 5.76 mmol), Cs2CO3 (2.36 g, 7.20 mmol), xantphos (0.22 g, 0.38 mmol) and 1,4-dioxane (30 ml) was charged in a sealed tube and degassed with argon gas for 15 min. Tetrakis(triphenylphosphine)palladium (0) (0.22 g, 0.19 mmol) was added and degassed for another 15 min and heated at 125° C. for 3 h. The reaction mixture was filtered and concentrated under reduced pressure to afford the crude compound. This was purified by column chromatography over neutral alumina using 0.5% MeOH in CHCl3 as eluent to afford 600 mg (62%) of 2-phenyl-2-aza-bicyclo[2.2.2]octan-3-one as pale yellow solid.

Workup

  1. additionwas charged in a sealed tube
  2. customdegassed with argon gas for 15 min
  3. customdegassed for another 15 min
  4. filtrationThe reaction mixture was filtered
  5. concentrationconcentrated under reduced pressure
  6. customto afford the crude compound
  7. customThis was purified by column chromatography over neutral alumina using 0.5% MeOH in CHCl3 as eluent

Sources & evidence

ORD record
ord-5741d3f7fcdb4c439e60ac05830070c3
Source dataset
uspto-grants-2015_06
Patent number
US09067888B2

Reaction notes

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