Lithium Chloride → (2S,3S)-2-benzyloxy-5-(2-(methylthio)phenyl)pentan-3-ol

HRID 1072053ノート

反応式

HRID 1072053 の反応式
[Mg:1].Cl[CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[S:10][CH3:11].[Cl-:12].[Li+].[CH2:14]([O:21][C@@H:22]([CH3:26])[CH:23]1[O:25][CH2:24]1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CCOCC.C1COCC1.[Cu](Cl)Cl.C(Cl)Cl>[CH3:11][S:10][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=1[CH2:3][Mg:1][Cl:12].[CH2:14]([O:21][C@H:22]([C@@H:23]([OH:25])[CH2:24][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[S:10][CH3:11])[CH3:26])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

参加物

10

反応物 4

HCID 433294Lithium ChlorideHCID 5462224MagnesiumHCID 124145821-(Chloromethyl)-2-(methylsulfanyl)benzeneHCID 57223577(3S)-3-benzyloxy-1,2-epoxybutane

生成物 2

HCID 69678578(2S,3S)-2-benzyloxy-5-(2-(methylthio)phenyl)pentan-3-ol収率 229.1%HCID 178503137HCID 178503137、化合物

試薬・触媒・溶媒 4

HCID 24014Cupric Chloride触媒HCID 3283Diethyl Ether溶媒2 回HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-70 °C

実験手順

2-Methylthiophenylmethylmagnesium chloride was prepared from magnesium turnings (654 mg) and 2-(chloromethyl)thioanisole (1.55 g) in ether (29 ml) by the method of J. Am. Chem. Soc. (1943) 65, 295. A solution of lithium chloride (38 mg) and copper(II) chloride (60 mg) in THF (2.8 ml) was added dropwise to the ethereal solution of the Grignard reagent followed by addition of a solution of (2RS,3S)-3-(benzyloxy)-1,2-epoxybutane (0.8 g) in ether (8 ml) below −60° C. The mixture was stirred at −70° C. for 1 h, and then allowed to warm to room temperature and stirred overnight. After cooling, the mixture was quenched with saturated aqueous ammonium chloride solution (22 ml). The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to give an oil. Column chromatography (CH2Cl2) over silica gel gave a pale brown oil of (2S,3S)-2-benzyloxy-5-(2-(methylthio)phenyl)pentan-3-ol (0.65 g, 45.8%).

後処理

  1. temperatureto warm to room temperature
  2. stirringstirred overnight
  3. temperatureAfter cooling
  4. customthe mixture was quenched with saturated aqueous ammonium chloride solution (22 ml)
  5. washThe organic layer was washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customto give an oil

出典と根拠

ORDレコード
ord-5bf87a5e41004f17acc5053d5743f43f
出典データセット
uspto-grants-2005_06
特許番号
US06908940B2

反応ノート

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