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

HRID 17280

Reaktionsgleichung

Reaktionsgleichung von HRID 17280
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[CH:69]=[CH:68][CH:67]=[C:66]([N+:70]([O-:72])=[O:71])[CH:65]=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.[CH3:73][N:74]([CH3:80])[C@H:75]1[CH2:79][CH2:78][NH:77][CH2:76]1.CC(C)([O-])C.[Na+].O.C(=O)(O)[O-].[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[CH:69]=[CH:68][CH:67]=[C:66]([N+:70]([O-:72])=[O:71])[CH:65]=3)[C:48]=2[N:77]2[CH2:78][CH2:79][C@H:75]([N:74]([CH3:80])[CH3:73])[CH2:76]2)[N:53]=1)([CH3:60])([CH3:59])[CH3:58]

Komponenten

9

Edukt 5

HCID 634876Binap, (A+-)-HCID 7019156(3S)-(-)-3-(Dimethylamino)pyrrolidineHCID 23676156Sodium t-butoxideHCID 685851247-Bromo-2-tert-butyl-5-methyl-6-(3-nitrophenyl)-1,3-benzoxazole-4-carbonitrileHCID 86585896Sodium bicarbonate water

Produkt 1

HCID 685844192-tert-butyl-7-[(3S)-3-(dimethylamino)pyrrolidin-1-yl]-5-methyl-6-(3-nitrophenyl)-1,3-benzoxazole-4-carbonitrile

Reagenzien, Katalysatoren, Lösungsmittel 3

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

Versuchsvorschrift

(S)-(−)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (180 mg, 0.29 mmol) was dissolved in toluene (8 ml) under heat, cooled to room temperature, then palladium(II) acetate (43 mg, 0.193 mmol) was added, followed by stirring for 5 minutes. 7-Bromo-2-tert-butyl-5-methyl-6-(3-nitrophenyl)-1,3-benzoxazole-4-carbonitrile (I-18) (400 mg, 0.966 mmol), (3S)-3-(dimethylamino)pyrrolidine (306 μl, 2.42 mmol), sodium tert-butoxide (260 mg, 2.71 mmol), toluene (5 ml) were successively put into it, followed by stirring at 80° C. for 13 hours. After cooling, brine (10 ml), saturated sodium bicarbonate water (25 ml) were added to the reaction liquid, the product was extracted with chloroform (25 ml×2). The organic layer was washed with saturated brine (10 ml×2), then dried over anhydrous magnesium sulfate, concentrated under reduced pressure. The residue was purified twice by silica gel column chromatography (chloroform:methanol=100:1) to obtain a fraction containing the entitled compound (35.1 mg) as a dark brown solid. Not further purified, this was used in the next reaction.

Aufarbeitung

  1. temperatureunder heat
  2. stirringby stirring at 80° C. for 13 hours
  3. temperatureAfter cooling
  4. extractionthe product was extracted with chloroform (25 ml×2)
  5. washThe organic layer was washed with saturated brine (10 ml×2)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified twice by silica gel column chromatography (chloroform:methanol=100:1)
  9. customto obtain a fraction
  10. customNot further purified
  11. customthis was used in the next reaction

Quellen und Nachweise

ORD-Eintrag
ord-443a24641306450dbcf9f66df4eb99e8
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07737166B2

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