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

HRID 749446Notes

Reaction equation

HRID 749446 reaction equation
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]

Participants

7

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

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)+.

Workup

  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)

Sources & evidence

ORD record
ord-e0b5ee0e216549ccb82c5b362f07fd5f
Source dataset
uspto-grants-2008_07
Patent number
US07402581B2

Reaction notes

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