Water → (-)-(3S,4E)-3-{[tert-Butyl(dimethyl)silyl]oxy}-4-methyl-5-(2-methyl-1,3-thiazol-4-yl)pent-4-en-1-ol

HRID 1700959Notes

Reaction equation

HRID 1700959 reaction equation
F.[Si]([O:9][CH2:10][CH2:11][C@H:12]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])/[C:13](/[CH3:21])=[CH:14]/[C:15]1[N:16]=[C:17]([CH3:20])[S:18][CH:19]=1)(C(C)(C)C)(C)C.C(=O)(O)[O-].[Na+].O>C(OCC)C.C(#N)C>[Si:23]([O:22][C@H:12](/[C:13](/[CH3:21])=[CH:14]/[C:15]1[N:16]=[C:17]([CH3:20])[S:18][CH:19]=1)[CH2:11][CH2:10][OH:9])([C:26]([CH3:28])([CH3:29])[CH3:27])([CH3:25])[CH3:24]

Participants

7

Reactant 4

HCID 962WaterHCID 14917Hydrofluoric Acid2×HCID 516892Sodium Bicarbonate2×HCID 10993911(S,4E)-1,3-Di-(tert-butyldimethylsilyloxy)-4-methyl-5-(2-methylthiazol-4-yl)-pent-4-ene

Product 1

HCID 10936330(-)-(3S,4E)-3-{[tert-Butyl(dimethyl)silyl]oxy}-4-methyl-5-(2-methyl-1,3-thiazol-4-yl)pent-4-en-1-olYield 84%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

20 ml of aqueous hydrofluoric acid (40%) at 0° C. is added to a vigorously stirred solution of (S,4E)-1,3-di-(tert-butyldimethylsilyloxy)-4-methyl-5-(2-methylthiazol-4-yl)-pent-4-ene 15 (13.255 g, 30.0 mmol) in 120 ml of diethyl ether and 120 ml of acetonitrile. Finely ground splinters of glass (133 mg) are added and the mixture is stirred for 2 h at 0° C. and analyzed by tic. If starting material can still be detected another portion of hydrofluoric acid (20 ml) is added and stirring is continued for 1 h. The reaction is quenched by carefully adding solid sodium bicarbonate (84.0 g, 1.0 mol) within 15 min at 0° C. After stirring for 30 min at 0° C. water is aaded until the salts dissolve (the pH is adjusted to 6-8 by further addition of sodium bicarbonate, if necessary). The mixture is extracted with dichloromethane (4×200 ml). The combined organic extracts are washed with brine (100 ml), dried over magnesium sulfate, and concentrated in vacuo. Purification of the residue by flash column chromatography (pentane/diethyl ether 4:1) affords (S,4E)-3-(tert-butyldimethylsilyloxy)-1-hydroxy-4-methyl-5-(2-methylthiazol-4-yl)-pent-4-ene 16 (8.255 g, 84%) as a viscous, colourless oil.

Workup

  1. additionis added
  2. stirringstirring
  3. waitis continued for 1 h
  4. customThe reaction is quenched
  5. dissolutiondissolve (the pH
  6. extractionThe mixture is extracted with dichloromethane (4×200 ml)
  7. washThe combined organic extracts are washed with brine (100 ml)
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated in vacuo
  10. customPurification of the residue by flash column chromatography (pentane/diethyl ether 4:1)

Sources & evidence

ORD record
ord-1e32ae40be014916a681b077a78b28b8
Source dataset
uspto-grants-2002_02
Patent number
US06350878B1

Reaction notes

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