Binap, (A+-)- → 2-tert-Butyl-7-[(3S)-3-(dimethylamino)pyrrolidin-1-yl]-6-(2-furyl)-5-methyl-1,3-benzoxazole-4-Carbonitrile

HRID 17270

Reaktionsgleichung

Reaktionsgleichung von HRID 17270
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:49]([C:64]2[O:65][CH:66]=[CH:67][CH:68]=2)=[C:50]([CH3:63])[C:51]([C:61]#[N:62])=[C:52]2[C:56]=1[O:55][C:54]([C:57]([CH3:60])([CH3:59])[CH3:58])=[N:53]2.[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.[Cl-].[Na+].O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:57]([C:54]1[O:55][C:56]2[C:52](=[C:51]([C:61]#[N:62])[C:50]([CH3:63])=[C:49]([C:64]3[O:65][CH:66]=[CH:67][CH:68]=3)[C:48]=2[N:73]2[CH2:74][CH2:75][C@H:71]([N:70]([CH3:76])[CH3:69])[CH2:72]2)[N:53]=1)([CH3:60])([CH3:59])[CH3:58]

Komponenten

8

Edukt 4

HCID 634876Binap, (A+-)-HCID 7019156(3S)-(-)-3-(Dimethylamino)pyrrolidineHCID 23676156Sodium t-butoxideHCID 685843857-Bromo-2-tert-butyl-6-(2-furyl)-5-methyl-1,3-benzoxazole-4-carbonitrile

Produkt 1

HCID 685851902-tert-Butyl-7-[(3S)-3-(dimethylamino)pyrrolidin-1-yl]-6-(2-furyl)-5-methyl-1,3-benzoxazole-4-CarbonitrileAusbeute 13,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 1140TolueneLösungsmittel2×HCID 57417360Sodium chloride; waterLösungsmittel

Versuchsvorschrift

(R)-(+)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (10.4 mg, 16.7 μmol) was dissolved in toluene (0.5 ml) under heat, cooled to room temperature, palladium(II) acetate (2.5 mg, 11.1 μmol) was added, followed by stirring for 1 minute. This was put into a toluene (0.5 ml) suspension of 7-bromo-2-tert-butyl-6-(2-furyl)-5-methyl-1,3-benzoxazole-4-carbonitrile (I-10) (40 mg, 111 μmol), (3S)-3-(dimethylamino)pyrrolidine (16.9 μl, 134 μmol), sodium tert-butoxide (15.0 mg, 156 μmol), followed by stirring at 80° C. for 17 hours. After cooling, brine (30 ml) was added to the reaction liquid, the product was extracted with chloroform (30 ml×3). The organic layer was washed with saturated brine (30 ml), then dried over anhydrous magnesium sulfate, concentrated under reduced pressure. The residue was purified by silica gel column chromatography (chloroform:methanol=1:0→100:1) to obtain the entitled compound (5.9 mg, 13%) as a yellow solid.

Aufarbeitung

  1. temperatureunder heat
  2. stirringby stirring at 80° C. for 17 hours
  3. temperatureAfter cooling
  4. extractionthe product was extracted with chloroform (30 ml×3)
  5. washThe organic layer was washed with saturated brine (30 ml)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (chloroform:methanol=1:0→100:1)

Quellen und Nachweise

ORD-Eintrag
ord-b73f497e241d4b91b14e1eb6dea555b1
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07737166B2

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