Acetonitrile → tert-Butyl {2-(4-cyanophenyl)-4-[(triisopropylsilyl)oxy]butyl}methylcarbamate

HRID 749446Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 749446
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:19][CH2:20][O:21][Si:22]([CH:29]([CH3:31])[CH3:30])([CH:26]([CH3:28])[CH3:27])[CH:23]([CH3:25])[CH3:24])[CH2:9][N:10]([CH3:18])[C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[CH:4][CH:3]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[C:54](#[N:56])C>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-]#N.[Zn+2].[C-]#N.CN(C=O)C>[C:54]([C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:19][CH2:20][O:21][Si:22]([CH:29]([CH3:30])[CH3:31])([CH:26]([CH3:28])[CH3:27])[CH:23]([CH3:24])[CH3:25])[CH2:9][N:10]([CH3:18])[C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[CH:4][CH:3]=1)#[N:56]

Komponenten

7

Edukt 3

HCID 6342AcetonitrileHCID 80271Tri-o-tolylphosphineHCID 86606885tert-Butyl {2-(4-bromophenyl)-4-[(triisopropylsilyl)oxy]butyl}methylcarbamate

Produkt 1

HCID 86606884tert-Butyl {2-(4-cyanophenyl)-4-[(triisopropylsilyl)oxy]butyl}methylcarbamateAusbeute 41 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

tert-Butyl {2-(4-bromophenyl)-4-[(triisopropylsilyl)oxy]butyl}methylcarbamate (1.16 g, 2.25 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.62 g, 0.68 mmol) and tri-o-tolylphosphine (1.03 g, 3.38 mmol) were mixed together with acetonitrile (3 mL) and DMF (3 mL) under argon. Zinc cyanide (0.16 g, 1.35 mmol) was added and the mixture was stirred at 81° C. for 24h and then concentrated. Ethyl acetate was added to the residue and the slurry was filtered through a micro filter. The solvent was removed by evaporation and the residue purified by flash chromatography (hexane-ether, 10:1). There was obtained 0.43 g, (41%) of tert-butyl {2-(4-cyanophenyl)-4-[(triisopropylsilyl)oxy]butyl}-methylcarbamate as a solid. 1H NMR (300 MHz, CDCl3): 0.9-1.1 (m, 21H), 1.4 (s, 9H), 1.7-1.9 (m, 2H), 2.7 (m, 3H), 3.2-3.6 (m, 5H), 7.3-7.4 (m, 2H), 7.5-7.6 (m, 2H); MS: m/z 361 (M+1)+.

Aufarbeitung

  1. concentrationconcentrated
  2. additionEthyl acetate was added to the residue
  3. filtrationthe slurry was filtered through a micro filter
  4. customThe solvent was removed by evaporation
  5. customthe residue purified by flash chromatography (hexane-ether, 10:1)

Quellen und Nachweise

ORD-Eintrag
ord-e0b5ee0e216549ccb82c5b362f07fd5f
Quelldatensatz
uspto-grants-2008_07
Patentnummer
US07402581B2

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