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

HRID 1072053Notes

Reaction equation

HRID 1072053 reaction equation
[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

Participants

10

Reactant 4

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

Product 2

HCID 69678578(2S,3S)-2-benzyloxy-5-(2-(methylthio)phenyl)pentan-3-olYield 229.1%HCID 178503137HCID 178503137, compound

Reagents, catalysts & solvents 4

HCID 24014Cupric ChlorideCatalystHCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

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%).

Workup

  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

Sources & evidence

ORD record
ord-5bf87a5e41004f17acc5053d5743f43f
Source dataset
uspto-grants-2005_06
Patent number
US06908940B2

Reaction notes

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