Binap, (A+-)- → HCID 52942144, compound

HRID 17545Notes

Reaction equation

HRID 17545 reaction equation
C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Br[C:48]1[C:53]2[CH:54]=[C:55]([C:57]([CH3:60])([CH3:59])[CH3:58])[O:56][C:52]=2[C:51]([C:61]#[N:62])=[CH:50][C:49]=1[C:63]1[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1.[CH3:69][N:70]([CH3:76])[C@H:71]1[CH2:75][CH2:74][NH:73][CH2:72]1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:57]([C:55]1[O:56][C:52]2[C:51]([C:61]#[N:62])=[CH:50][C:49]([C:63]3[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=3)=[C:48]([N:73]3[CH2:74][CH2:75][C@H:71]([N:70]([CH3:76])[CH3:69])[CH2:72]3)[C:53]=2[CH:54]=1)([CH3:60])([CH3:59])[CH3:58]

Participants

8

Reactant 4

HCID 634876Binap, (A+-)-HCID 7019156(3S)-(-)-3-(Dimethylamino)pyrrolidineHCID 23676156Sodium t-butoxideHCID 68586325HCID 68586325, compound

Product 1

HCID 52942144HCID 52942144, compoundYield 33%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent2×

Procedure

(R)-(+)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (65.9 mg, 106 μmol) was dissolved under heat in toluene (1.5 ml), then cooled to room temperature, and palladium(II) acetate (15.8 mg, 70.6 μmol) was added, followed by stirring for 1 minute. 4-Bromo-2-tert-butyl-7-cyano-5-phenyl-1-benzofuran (I-258) (500 mg, 1.41 mmol), (3S)-3-(dimethylamino)pyrrolidine (215 μl, 1.69 mmol), sodium tert-butoxide (190 mg, 1.98 mmol) and toluene (1.5 ml) were successively put into it, followed by stirring at 80° C. for 14 hours. Water (30 ml) was added to the reaction liquid, the product was extracted with chloroform (50 ml×3). The organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure. The residue was purified twice by silica gel column chromatography (chloroform:methanol=200:1) to obtain the entitled compound (180 mg, 33%) as a yellow solid.

Workup

  1. stirringby stirring at 80° C. for 14 hours
  2. extractionthe product was extracted with chloroform (50 ml×3)
  3. washThe organic layer was washed with saturated brine (50 ml)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified twice by silica gel column chromatography (chloroform:methanol=200:1)

Sources & evidence

ORD record
ord-5960e71201fb4f85bbd7b014b7ff78e0
Source dataset
uspto-grants-2010_06
Patent number
US07737166B2

Reaction notes

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