Ammonium Chloride → 1,1-Dimethylethyl 4-hydroxy-4-(3-trimethylsilyloxypropynyl)-1-piperidinecarboxylate

HRID 747021Notes

Reaction equation

HRID 747021 reaction equation
C([Mg]Br)C.[CH3:5][Si:6]([CH3:12])([CH3:11])[O:7][CH2:8][C:9]#[CH:10].[N:13]1([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:18][CH2:17][C:16](=[O:19])[CH2:15][CH2:14]1.[Cl-].[NH4+]>O1CCCC1>[OH:19][C:16]1([C:10]#[C:9][CH2:8][O:7][Si:6]([CH3:12])([CH3:11])[CH3:5])[CH2:15][CH2:14][N:13]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:18][CH2:17]1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 79696Silane, trimethyl(2-propyn-1-yloxy)-HCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 178418443HCID 178418443, compound

Product 1

HCID 219551731,1-Dimethylethyl 4-hydroxy-4-(3-trimethylsilyloxypropynyl)-1-piperidinecarboxylateYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

Ethyl magnesium bromide in tetrahydrofuran (55 mL, 1M, 55 mmol) was slowly added to a solution of trimethyl(prop-2-yn-1-yloxy)silane in tetrahydrofuran (40 mL) maintaining a temperature of 0° C. After the complete addition the mixture was stirred at ambient temperature for 45 min before a solution of tert-butyl piperidin-4-one-1-carboxylate (10 g, 50 mmol) in tetrahydrofuran (40 mL) was slowly added at 0° C. Subsequently the reaction mixture was stirred for 18 h at ambient temperature. Then saturated ammonium chloride solution was added and the mixture was stirred vigorously until the dissolution of all solids. The phases were separated and the aqueous was extracted with ethyl acetate. The combined organic phases were washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 16.42 g of desired product (96%) as a yellow oil.

Workup

  1. additionAfter the complete addition the mixture
  2. additionwas slowly added at 0° C
  3. stirringthe mixture was stirred vigorously until the dissolution of all solids
  4. customThe phases were separated
  5. extractionthe aqueous was extracted with ethyl acetate
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-46bd9f710a064df9b1f6306f4d1e65f4
Source dataset
uspto-grants-2008_07
Patent number
US07393858B2

Reaction notes

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