5-Bromoacenaphthene → (3R)-1-(1,2-Dihydro-5-acenaphthylenyl)-3-methylpiperazine

HRID 2056731Notes

Reaction equation

HRID 2056731 reaction equation
[CH3:1][C@@H:2]1[CH2:7][NH:6][CH2:5][CH2:4][NH:3]1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+].Br[C:61]1[C:71]2[C:72]3[C:64]([CH2:65][CH2:66][C:67]=3[CH:68]=[CH:69][CH:70]=2)=[CH:63][CH:62]=1>C1(C)C=CC=CC=1.ClCCl.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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:65]1[C:64]2=[C:72]3[C:71](=[CH:61][CH:62]=[CH:63]2)[C:70]([N:6]2[CH2:5][CH2:4][NH:3][C@H:2]([CH3:1])[CH2:7]2)=[CH:69][CH:68]=[C:67]3[CH2:66]1

Participants

8

Reactant 4

HCID 749235-BromoacenaphtheneHCID 634876Binap, (A+-)-HCID 73304342-Methylpiperazine, (R)-HCID 23676156Sodium t-butoxide

Product 1

HCID 69307361(3R)-1-(1,2-Dihydro-5-acenaphthylenyl)-3-methylpiperazine

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 2-(R)-methylpiperazine (0.124 g, 1.1 mmol), tris(dibenzylideneacetone)dipalladium(0) (49 mg, 0.05 mmol), rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (69 mg, 0.10 mmol) and sodium tert-butoxide (0.148 g, 1.5 mmol) were stirred in toluene (50 mL) under nitrogen for 15 min to give a blood red solution. 5-Bromo-1,2-dihydroacenaphthylene (0.256 g, 1.1 mmol) was added, the solution stirred under nitrogen and heated at reflux for 3 h. The mixture was cooled, diluted with dichloromethane and filtered through celite. The organic phase was washed with water, dried (MgSO4), filtered and evaporated in vacuo. The crude product was taken forward to the next step without further purification.

Workup

  1. customto give a blood red solution
  2. temperatureheated
  3. temperatureat reflux for 3 h
  4. temperatureThe mixture was cooled
  5. filtrationfiltered through celite
  6. washThe organic phase was washed with water
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customevaporated in vacuo
  10. customThe crude product was taken forward to the next step without further purification

Sources & evidence

ORD record
ord-a244e5c7cab34822b5f2eb0206c39364
Source dataset
uspto-grants-2008_02
Patent number
US07335660B2

Reaction notes

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