Dimethylformamide → tert-Butyl 1-(4-cyanophenyl)-3,3-dimethyl-1-oxobutan-2-ylcarbamate

HRID 535777ノート

反応式

HRID 535777 の反応式
Cl[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:22])[CH:9]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[C:10]([CH3:13])([CH3:12])[CH3:11])=[CH:4][CH:3]=1.[CH3:23][N:24](C=O)C>O.[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:23]([C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:22])[CH:9]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[C:10]([CH3:13])([CH3:12])[CH3:11])=[CH:4][CH:3]=1)#[N:24]

参加物

6

反応物 2

HCID 6228DimethylformamideHCID 684053282-(Boc-amino)-2-t-butyl-1-(4-chlorophenyl)ethanone

生成物 1

HCID 68404944tert-Butyl 1-(4-cyanophenyl)-3,3-dimethyl-1-oxobutan-2-ylcarbamate収率 43%

試薬・触媒・溶媒 3

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒

反応条件

温度
130 °C

実験手順

tert-Butyl 1-(4-chlorophenyl)-3,3-dimethyl-1-oxobutan-2-ylcarbamate (Example 2a, 2.30 g, 7.06 mmol) and Zn(CN)2 (0.87 g, 7.4 mmol) were dissolved in DMF (20 mL) under N2 (g). Pd(PPh3)4 (0.86 g, 0.74 mmol) was added and the mixture was heated at 130° C. overnight. The mixture was cooled to rt, diluted with water and extracted with EtOAc. The organic phase was washed with brine, dried over Na2SO4 and evaporated. The product was purified on a silica column (EtOAc:hexane 1:10) to give tert-butyl 1-(4-cyanophenyl)-3,3-dimethyl-1-oxobutan-2-ylcarbamate (961 mg, 43%). tert-Butyl 1-(4-cyanophenyl)-3,3-dimethyl-1-oxobutan-2-ylcarbamate (961 mg, 3.04 mmol) was dissolved in 1.25 M HCl in MeOH at 0° C. and the mixture was stirred at rt for 8 h. The solvent was removed and the residue dried in vacuo to give 4-(2-amino-3,3-dimethyl-butanoyl)-benzonitrile hydrochloride (110 mg, 93%).

後処理

  1. temperatureThe mixture was cooled to rt
  2. extractionextracted with EtOAc
  3. washThe organic phase was washed with brine
  4. dry with materialdried over Na2SO4
  5. customevaporated
  6. customThe product was purified on a silica column (EtOAc:hexane 1:10)

出典と根拠

ORDレコード
ord-ec91184890b740d5a6e6411a50334ebe
出典データセット
uspto-grants-2014_10
特許番号
US08859556B2

反応ノート

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