Sodium bis(trimethylsilyl)amide → HCID 68616384, compound

HRID 2405810Notes

Reaction equation

HRID 2405810 reaction equation
[CH3:1][Si]([N-][Si](C)(C)C)(C)C.[Na+].[CH3:11][O:12][C:13]([C:15]1([NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:17][CH:16]1[CH2:18][CH:19]=O)=[O:14]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH3:11][O:12][C:13]([C:15]1([NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:17][CH:16]1[CH2:18][CH:19]=[CH2:1])=[O:14]

Participants

5

Reactant 2

HCID 2724254Sodium bis(trimethylsilyl)amideHCID 76605109HCID 76605109, compound

Product 1

HCID 68616384HCID 68616384, compound

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

Methyltriphenylphosphonium bromide (4.6 mmol) was suspended in THF (10 mL) at room temperature. NaHMDS (1.0 M in THF, 4.1 mmol) was added dropwise at room temperature to produce a dark yellow turbid solution which was allowed to stir for 30 min. A THF (6 mL) solution of 1-tert-butoxycarbonylamino-2-(2-oxo-ethyl)-cyclopropanecarboxylic acid methyl ester was added dropwise to the ylide solution and allowed to age at room temperature for 30 min. The reaction was partitioned between EtOAc and saturated NH4Cl. The aqueous layer was extracted with EtOAc (3×10 mL) and the combined organics washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo. Purification by column chromatography on SiO2 (0→10% EtOAc/hex) afforded 2-allyl-1-tert-butoxycarbonylamino-cyclopropanecarboxylic acid methyl ester as a colorless film (0.070 g, 15%). (1H-NMR (300 MHz, CDCl3): δ 5.90-5.72 (m, 1H); 5.14 (br s, 1H); 5.08-4.94 (m, 2H); 3.71 (s, 3H); 2.34 (m, 2H); 1.55 (m, 2H); 1.45 (s, 9H), 1.37 (m, 1H)).

Workup

  1. customto produce a dark yellow turbid solution which
  2. waitallowed to age at room temperature for 30 min
  3. customThe reaction was partitioned between EtOAc and saturated NH4Cl
  4. extractionThe aqueous layer was extracted with EtOAc (3×10 mL)
  5. washthe combined organics washed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated in vacuo
  8. customPurification by column chromatography on SiO2 (0→10% EtOAc/hex)

Sources & evidence

ORD record
ord-0cf41cbc3b954731b14a66965570d0d0
Source dataset
uspto-grants-2014_08
Patent number
US08809267B2

Reaction notes

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