1,3-Dibromobenzene → HCID 57421406, compound

HRID 641937Notes

Reaction equation

HRID 641937 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[CH:3]=1.[O:9]1[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]1[O:15][CH:16]1[CH2:20][CH2:19][NH:18][CH2:17]1.C([O-])([O-])=O.[Cs+].[Cs+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[Br:8][C:4]1[CH:3]=[C:2]([N:18]2[CH2:19][CH2:20][CH:16]([O:15][CH:10]3[CH2:11][CH2:12][CH2:13][CH2:14][O:9]3)[CH2:17]2)[CH:7]=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 79271,3-DibromobenzeneHCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 64876053-(oxan-2-yloxy)pyrrolidine

Product 1

HCID 57421406HCID 57421406, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

Into a 250 mL 3-necked round bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 1,3-dibromobenzene (7.0 g, 29.91 mmol) in toluene (100 mL). To this was added 3-(tetrahydro-2H-pyran-2-yloxy)pyrrolidine (5.6 g, 32.75 mmol). Addition of Pd(OAc)2 (66.9 mg, 0.30 mmol) was next. This was followed by the addition of Cs2CO3 (24.27 g, 74.49 mmol). To the mixture was added BINAP (556 mg, 0.89 mmol). The resulting solution was allowed to react, with stirring, overnight while the temperature was maintained at reflux in a bath of oil. The reaction progress was monitored by TLC (ethyl acetate/petroleum ether=1:5). A filtration was performed. The filter cake was washed 3 times with 100 mL of brine. The mixture was dried over MgSO4. The residue was purified by eluting through a column with a 1:100 ethyl acetate/petroleum ether solvent system. This resulted in 1.36 g (13%) of 1-(3-bromophenyl)-3-(tetrahydro-2H-pyran-2-yloxy)pyrrolidine as a yellow liquid.

Workup

  1. customInto a 250 mL 3-necked round bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. customto react
  4. temperaturewas maintained
  5. temperatureat reflux in a bath of oil
  6. filtrationA filtration
  7. washThe filter cake was washed 3 times with 100 mL of brine
  8. dry with materialThe mixture was dried over MgSO4
  9. customThe residue was purified
  10. washby eluting through a column with a 1:100 ethyl acetate/petroleum ether solvent system
  11. customThis resulted in 1.36 g (13%) of 1-(3-bromophenyl)-3-(tetrahydro-2H-pyran-2-yloxy)pyrrolidine as a yellow liquid

Sources & evidence

ORD record
ord-165752307ec14a6d8e0103930a609a9d
Source dataset
uspto-grants-2010_04
Patent number
US07696229B2

Reaction notes

Loading…