Dimethylformamide → tert-butyl (2S)-2-(4-cyanophenyl)morpholine-4-carboxylate

HRID 710247ノート

反応式

HRID 710247 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([C@@H:8]2[O:13][CH2:12][CH2:11][N:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:9]2)=[CH:4][CH:3]=1.[CH3:21][N:22](C)C=O>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-]#N.[Zn+2].[C-]#N>[C:21]([C:2]1[CH:7]=[CH:6][C:5]([C@@H:8]2[O:13][CH2:12][CH2:11][N:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:9]2)=[CH:4][CH:3]=1)#[N:22]

参加物

5

反応物 2

HCID 6228DimethylformamideHCID 58097875tert-butyl (2S)-2-(4-bromophenyl)morpholine-4-carboxylate

生成物 1

HCID 66861409tert-butyl (2S)-2-(4-cyanophenyl)morpholine-4-carboxylate収率 69%

試薬・触媒・溶媒 2

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

反応条件

温度
85 °C

実験手順

A mixture of (S)-tert-butyl 2-(4-bromophenyl)morpholine-4-carboxylate (400 mg, 1.17 mmol), tetrakis(triphenylphosphine)palladium(0) (405 mg, 0.35 mmol) and zinc cyanide (206 mg, 1.75 mmol) in dimethylformamide (6 ml) was degassed with argon and heated in a closed tube at 85° C. on a Büchi shaker overnight. After cooling water (30 ml) was added, and the reaction mixture was extracted with ethyl acetate (50 ml). The aqueous phase was re-extracted with ethyl acetate (50 ml). The combined organic layers were re-extracted with conc. Sodium chloride solution, dried (MgSO4) and evaporated. The residue was purified by flash chromatography (20 g silica gel, 10% ethyl acetate in heptane) to yield a white solid (233 mg, 69%). MS (ISP): 289.1 ([M+H]+), 306.2 ([M+NH4]+).

後処理

  1. customwas degassed with argon
  2. temperatureAfter cooling water (30 ml)
  3. additionwas added
  4. extractionthe reaction mixture was extracted with ethyl acetate (50 ml)
  5. extractionThe aqueous phase was re-extracted with ethyl acetate (50 ml)
  6. extractionThe combined organic layers were re-extracted with conc. Sodium chloride solution
  7. dry with materialdried (MgSO4)
  8. customevaporated
  9. customThe residue was purified by flash chromatography (20 g silica gel, 10% ethyl acetate in heptane)

出典と根拠

ORDレコード
ord-6aab78deb6fd45be876d214dd2156f5c
出典データセット
uspto-grants-2015_11
特許番号
US09181230B2

反応ノート

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