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Potassium Carbonate → 2-{[3'-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)-5-methyl-3-biphenylyl]methyl}-1H-isoindole-1,3(2H)-dione

HRID 662057
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 662057
C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[K+].[K+].Br[C:27]1[CH:28]=[C:29]([CH2:34][N:35]2[C:43](=[O:44])[C:42]3[C:37](=[CH:38][CH:39]=[CH:40][CH:41]=3)[C:36]2=[O:45])[CH:30]=[C:31]([CH3:33])[CH:32]=1.[CH3:46][C:47]([Si:50]([CH3:63])([CH3:62])[O:51][CH2:52][C:53]1[CH:54]=[C:55](B(O)O)[CH:56]=[CH:57][CH:58]=1)([CH3:49])[CH3:48]>O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:46][C:47]([Si:50]([CH3:63])([CH3:62])[O:51][CH2:52][C:53]1[CH:54]=[C:55]([C:27]2[CH:32]=[C:31]([CH3:33])[CH:30]=[C:29]([CH2:34][N:35]3[C:43](=[O:44])[C:42]4[C:37](=[CH:38][CH:39]=[CH:40][CH:41]=4)[C:36]3=[O:45])[CH:28]=2)[CH:56]=[CH:57][CH:58]=1)([CH3:49])[CH3:48]
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Komponenten

7

Edukt 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 57813382[3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acidHCID 578134412-[(3-bromo-5-methylphenyl)methyl]-1H-isoindole-1,3(2H)-dione

Produkt 1

HCID 578133262-{[3'-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)-5-methyl-3-biphenylyl]methyl}-1H-isoindole-1,3(2H)-dione
Ausbeute 68 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

Pd(OAc)2 (102.0 mg, 0.45 mmol, 0.03 eq.), PPh3 (476.4 mg, 1.82 mmol, 0.12 eq.), K2CO3 (3.14 g, 22.7 mmol, 1.50 eq.) and 2-[(3-bromo-5-methylphenyl)methyl]-1H-isoindole-1,3(2H)-dione (5.00 g, 13.1 mmol, 1.00 eq.) were suspended in anhydrous 1,4-dioxane (30 mL) under nitrogen. After the mixture was heated to 60° C. for 10 min, [3-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid (4.84 g, 18.2 mmol, 1.20 eq.) was added. Then the reaction mixture was stirred over night at 100° C. After cooling it to room temperature, the solvent was removed under reduced pressure. Then water (25 mL) was added, extracted with CH2Cl2 twice (70 mL, 50 mL). The organic layer was washed with brine (20 mL×2), dried over anhydrous Na2SO4. After the solvent was removed, the crude product was purified on silica column chomatography, eluting with PE/EA (20:1 to 10:1), to give 4.2 g of product, 2-{[3′-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-5-methyl-3-biphenylyl]methyl}-1H-isoindole-1,3(2H)-dione, as a colorless liquid (yield: 59%). 1H NMR (400 MHz, CDCl3) δ 0.11 (s, 6H), 0.95 (s, 9H), 2.38 (s, 3H), 4.79 (s, 2H), 4.87 (s, 2H), 7.23 (s, 1H), 7.31-7.49 (m, 6H), 7.70-7.72 (m, 2H), 7.84-7.86 (m, 2H).

Aufarbeitung

  1. temperatureAfter cooling it to room temperature
  2. customthe solvent was removed under reduced pressure
  3. additionThen water (25 mL) was added
  4. extractionextracted with CH2Cl2 twice (70 mL, 50 mL)
  5. washThe organic layer was washed with brine (20 mL×2)
  6. dry with materialdried over anhydrous Na2SO4
  7. customAfter the solvent was removed
  8. customthe crude product was purified on silica column chomatography
  9. washeluting with PE/EA (20:1 to 10:1)

Quellen und Nachweise

ORD-Eintrag
ord-5b0094dbdd474b01bd411278fb556628
Quelldatensatz
uspto-grants-2011_12
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08084449B2

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