Trimethylsilylacetylene → 1-Allyloxycarbonyl-4-hydroxy-2-methoxycarbonyl-4-trimethylsilylethynylpyrrolidine

HRID 1029622Notes

Reaction equation

HRID 1029622 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].C([Li])CCC.[CH2:12]([O:15][C:16]([N:18]1[CH2:22][C:21](=[O:23])[CH2:20][C@H:19]1[C:24]([O:26][CH3:27])=[O:25])=[O:17])[CH:13]=[CH2:14]>O1CCCC1.[Cl-].[NH4+].C(OCC)(=O)C>[CH2:12]([O:15][C:16]([N:18]1[CH2:22][C:21]([OH:23])([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[CH2:20][CH:19]1[C:24]([O:26][CH3:27])=[O:25])=[O:17])[CH:13]=[CH2:14]

Participants

7

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 15117229(2S)-1-allyloxycarbonyl-2-methoxycarbonyl-4-oxopyrrolidineHCID 178418339Butyllithium

Product 1

HCID 151172301-Allyloxycarbonyl-4-hydroxy-2-methoxycarbonyl-4-trimethylsilylethynylpyrrolidineYield 57.7%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolventHCID 25517Ammonium ChlorideSolvent

Procedure

To a solution of trimethylsilylacetylene (5 g) in tetrahydrofuran (60 ml) was added n-butyllithium (32 ml) slowly and dropwise at -50° C. After completion of the dropwise addition, the mixture was stirred at -50° C. for 30 minutes, at the end of which time a tetrahydrofuran solution (10 ml) of (2S)-1-allyloxycarbonyl-2-methoxycarbonyl-4-oxopyrrolidine (10 g) was added below -50° C. The mixture was stirred for 1 hour and, then, diluted with saturated aqueous ammonium chloride solution and ethyl acetate. After standing, the aqueous layer was separated and extracted with ethyl acetate twice and the organic layers were combined, washed successively with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, water and aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. Finally the solvent was distilled off under reduced pressure to give 1-allyloxycarbonyl-4-hydroxy-2-methoxycarbonyl-4-trimethylsilylethynylpyrrolidine (8.26 g).

Workup

  1. customdropwise at -50° C
  2. additionAfter completion of the dropwise addition
  3. additionwas added below -50° C
  4. customthe aqueous layer was separated
  5. extractionextracted with ethyl acetate twice
  6. washwashed successively with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, water and aqueous sodium chloride solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationFinally the solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-bb574fce8317409592793ac3c7124bce
Source dataset
uspto-grants-1992_04
Patent number
US05102877

Reaction notes

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