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

HRID 749446ノート

反応式

HRID 749446 の反応式
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]

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 6228Dimethylformamide溶媒

実験手順

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)+.

後処理

  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)

出典と根拠

ORDレコード
ord-e0b5ee0e216549ccb82c5b362f07fd5f
出典データセット
uspto-grants-2008_07
特許番号
US07402581B2

反応ノート

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