Benzophenone imine → 2-(Benzhydrylideneamino)-7-(5-methylhexahydropyrrolo[3,4-c]pyrrol-2-yl)-fluoren-9-one

HRID 553059Notes

Reaction equation

HRID 553059 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([N:15]4[CH2:22][CH:21]5[CH:17]([CH2:18][N:19]([CH3:23])[CH2:20]5)[CH2:16]4)=[CH:9][CH:10]=3)[C:5](=[O:24])[C:4]=2[CH:3]=1.[C:25](=[NH:38])([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=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+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:25](=[N:38][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([N:15]4[CH2:22][CH:21]5[CH:17]([CH2:18][N:19]([CH3:23])[CH2:20]5)[CH2:16]4)=[CH:9][CH:10]=3)[C:5](=[O:24])[C:4]=2[CH:3]=1)([C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

7

Reactant 4

HCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 671645522-Bromo-7-(5-methylhexahydropyrrolo[3,4-c]pyrrol-2-yl)-fluoren-9-one

Product 1

HCID 866211422-(Benzhydrylideneamino)-7-(5-methylhexahydropyrrolo[3,4-c]pyrrol-2-yl)-fluoren-9-oneYield 100%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of the product of Example 61A (332 mg, 0.867 mmol), benzophenone imine (180 μL, 1.07 mmol; Aldrich), tris(dibenzylideneacetone)dipalladium (0) (Pd2 dba3; 32 mg, 0.035 mmol; Alfa), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP; 54 mg, 0.087 mmol; Strem) and sodium tert-butoxide (125 mg, 1.30 mmol; Aldrich) in 5 mL toluene was flushed with nitrogen and heated at 90° C. for 18 h. The reaction mixture was cooled to ambient temperature and filtered through diatomaceous earth, rinsing with EtOAc. After concentrating the solution under reduced pressure, the residue was purified by column chromatography (90 g silica gel, 1-12% gradient of NH4OH-MeOH (1:10) in CH2Cl2) to afford the title compound, which was slightly impure (489 mg, >100% yield): MS (DCI/NH3): m/z 484 (M+1)+.

Workup

  1. customwas flushed with nitrogen
  2. temperatureThe reaction mixture was cooled to ambient temperature
  3. filtrationfiltered through diatomaceous earth
  4. washrinsing with EtOAc
  5. concentrationAfter concentrating the solution under reduced pressure
  6. customthe residue was purified by column chromatography (90 g silica gel, 1-12% gradient of NH4OH-MeOH (1:10) in CH2Cl2)

Sources & evidence

ORD record
ord-6ee5658e142f4d8d91128ffab70dc3a0
Source dataset
uspto-grants-2011_05
Patent number
US07951791B2

Reaction notes

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