Cesium carbonate → HCID 53949865, compound

HRID 1947669Notes

Reaction equation

HRID 1947669 reaction equation
[N:1]1([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:6][CH2:5][CH:4]([CH:7]2[CH2:12][CH2:11][NH:10][CH2:9][CH2:8]2)[CH2:3][CH2:2]1.Br[C:21]1[CH:30]=[CH:29][C:24]([C:25]([O:27][CH3:28])=[O:26])=[CH:23][CH:22]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CN1C(=O)CCC1>ClCCl.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:16]([O:15][C:13]([N:1]1[CH2:6][CH2:5][CH:4]([CH:7]2[CH2:12][CH2:11][N:10]([C:21]3[CH:30]=[CH:29][C:24]([C:25]([O:27][CH3:28])=[O:26])=[CH:23][CH:22]=3)[CH2:9][CH2:8]2)[CH2:3][CH2:2]1)=[O:14])([CH3:19])([CH3:18])[CH3:17]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 12081Methyl 4-bromobenzoateHCID 13387N-methyl-2-pyrrolidoneHCID 117475994,4'-Bipiperidine, 1-boc protected

Product 1

HCID 53949865HCID 53949865, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
90 °C

Procedure

A 100 mL reaction flask was charged with tert-butyl 4,4′-bipiperidine-1-carboxylate (1.14 g; 4.25 mmol), methyl 4-bromobenzoate (913 mg; 4.25 mmol), cesium carbonate (4.15 g; 12.74 mmol), Pd(OAc)2 (48 mg; 0.212 mmol) and 2-(diphenylphosphino)-2′-(N-N-dimethylamino)biphenyl (162 mg; 0.425 mmol). NMP (outgassed by bubbling with nitrogen for 10 min; 10 mL) was added and the mixture stirred at 90° C. for 18 hr. The mixture was diluted with dichloromethane (100 mL) and filtered through Celite. The filtrate was washed with water (4×25 mL). The organic was dried over magnesium sulfate, filtered and evaporated to a solid. The solid was digested at reflux (MTBE). After cooling, the white solid was recovered by filtration. The filtrate was evaporated and chromatographed (Horizon; 0% to 100% EtOAc/hex; linear gradient). The fractions containing the desired compound were recovered and combined with the solid to give the title compound.

Workup

  1. customA 100 mL reaction flask
  2. filtrationfiltered through Celite
  3. washThe filtrate was washed with water (4×25 mL)
  4. dry with materialThe organic was dried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated to a solid
  7. temperatureat reflux (MTBE)
  8. temperatureAfter cooling
  9. filtrationthe white solid was recovered by filtration
  10. customThe filtrate was evaporated
  11. customchromatographed (Horizon; 0% to 100% EtOAc/hex; linear gradient)
  12. additionThe fractions containing the desired compound
  13. customwere recovered

Sources & evidence

ORD record
ord-89e1972e31de4435917670a5ee2bbb4e
Source dataset
uspto-grants-2013_03
Patent number
US08399485B2

Reaction notes

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