Imidazole → Tributylphosphine oxide

HRID 1039729

反応式

HRID 1039729 の反応式
[Si:1]([O:8][C@@H:9]([CH:19]1[CH2:21][N@@:20]1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[NH:29]1[CH:33]=[CH:32][N:31]=[CH:30]1.[CH2:34]([P:38]([CH2:43][CH2:44][CH2:45][CH3:46])[CH2:39][CH2:40][CH2:41][CH3:42])[CH2:35][CH2:36][CH3:37].[H-].[Na+]>C1(C)C=CC=CC=1>[Si:1]([O:8][C@H:9]([CH2:10][O:11][Si:12]([C:15]([CH3:16])([CH3:18])[CH3:17])([CH3:13])[CH3:14])[C@@H:19]([NH:20][C:22](=[O:23])[O:24][C:25]([CH3:26])([CH3:27])[CH3:28])[CH2:21][N:29]1[CH:33]=[CH:32][N:31]=[CH:30]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2].[CH2:43]([P:38](=[O:8])([CH2:34][CH2:35][CH2:36][CH3:37])[CH2:39][CH2:40][CH2:41][CH3:42])[CH2:44][CH2:45][CH3:46]

参加物

7

反応物 4

HCID 795ImidazoleHCID 13831TributylphosphineHCID 24758Sodium hydrideHCID 86635713(S)-tert-butyl 2-((S)-1,2-bis(tert-butyldimethylsilyloxy)ethyl)aziridine-1-carboxylate

生成物 2

HCID 13138Tributylphosphine oxideHCID 57950888tert-butyl (2S,3S)-3,4-bis(tert-butyldimethylsilyloxy)-1-(1H-imidazol-1-yl)butan-2-ylcarbamate

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

A solution of (5)-tert-butyl 2-((S)-1,2-bis(tert-butyldimethylsilyloxy)ethyl)aziridine-1-carboxylate (0.740 g, 1.7 mmol) and 1H-imidazole (0.35 g, 5.1 mmol) in 3 mL toluen was thoroughly degassed and treated with tributylphosphine (0.42 ml, 1.7 mmol). The reaction mixture was heated to reflux and allowed to stir for 3 hours. NaH (60% dispersion in mineral oil) (0.069 g, 2.9 mmol) was added and the reaction mixture was allowed to stir at 110° C. overnight. The reaction mixture was quenched with saturated NH4Cl solution and diluted with EtOAc. The reaction mixture was washed with water then brine. The organics were dried over MgSO4 and concentrated in vacuo. Purification of the crude residue by column chromatography gave tert-butyl (2S,3S)-3,4-bis(tert-butyldimethylsilyloxy)-1-(1H-imidazol-1-yl)butan-2-ylcarbamate with tributylphosphine oxide as the major impurity. This material was used without further purification.

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux
  3. stirringto stir at 110° C. overnight
  4. customThe reaction mixture was quenched with saturated NH4Cl solution
  5. additiondiluted with EtOAc
  6. washThe reaction mixture was washed with water
  7. dry with materialThe organics were dried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customPurification of the crude residue by column chromatography

出典と根拠

ORDレコード
ord-fca6ca29bd5b4a0cb7261eb70aaef559
出典データセット
uspto-grants-2013_10
特許番号
US08552181B2

関連ノート

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