Cesium carbonate → HCID 68379404, compound

HRID 1410071Notes

Reaction equation

HRID 1410071 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1.[CH3:11][C@H:12]1[CH2:16][CH2:15][CH2:14][NH:13]1.C([O-])([O-])=O.[Cs+].[Cs+].CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[CH3:11][C@H:12]1[CH2:16][CH2:15][CH2:14][N:13]1[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 11457Benzene, 1-bromo-3-nitro-HCID 6999702(2S)-2-methylpyrrolidineHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl

Product 1

HCID 68379404HCID 68379404, compoundYield 58.2%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 1-bromo-3-nitrobenzene (2.02 g, 0.01 mol) and (S)-2-methylpyrrolidine (1.02 g, 0.012 mol) in 20 mL of 1,4-dioxane was added Cs2CO3 (6.5 g, 0.02 mol) followed by Pd(dba)2 (1.15 g, 0.002 mmol) and X-Phos (476 mg, 0.001 mol) under nitrogen with stirring. The mixture was refluxed for 16 hours under nitrogen. After cooled, the mixture was filtered, and then the filtrate was evaporated by rotary evaporation. The residue was diluted with water and extracted with EtOAc (3×30 mL). The organic layer was washed with brine and dried over Na2SO4. After filtration and concentration, the residue was purified by column chromatography on silica gel eluting with (petroleum ether:EtOAc=10:1) to give (S)-2-methyl-1-(3-nitrophenyl)pyrrolidine (1.2 g, 57%) as an oil. 1H NMR (300 MHz, CDCl3) δ 7.47-7.44 (m, 1H), 7.37-7.35 (m, 1H), 7.32-7.27 (m, 1H), 6.86-6.83 (m, 1H), 3.95-3.91 (m, 1H), 3.50-3.44 (m, 1H), 3.26-3.18 (m, 1H), 2.18-1.99 (m, 3H), 1.80-1.72 (m, 1H), 1.21 (d, 2H, J=6.3 Hz). LC-MS: 207 [M+H]+, tR=1.75 min.

Workup

  1. temperatureThe mixture was refluxed for 16 hours under nitrogen
  2. temperatureAfter cooled
  3. filtrationthe mixture was filtered
  4. customthe filtrate was evaporated by rotary evaporation
  5. additionThe residue was diluted with water
  6. extractionextracted with EtOAc (3×30 mL)
  7. washThe organic layer was washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationAfter filtration and concentration
  10. customthe residue was purified by column chromatography on silica gel eluting with (petroleum ether:EtOAc=10:1)

Sources & evidence

ORD record
ord-252c8113b70b4323928696d2f0cda005
Source dataset
uspto-grants-2014_12
Patent number
US08921383B2

Reaction notes

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