Triphenylphosphine → (S)-4-Azido-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-L-proline, methyl ester

HRID 851429Notes

Reaction equation

HRID 851429 reaction equation
O[CH:2]1[CH2:6][N:5]([C:7](=[O:24])[CH2:8][P:9]([O:21][CH2:22][CH3:23])([CH2:11][CH2:12][CH2:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:10])[C@H:4]([C:25]([O:27][CH3:28])=[O:26])[CH2:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH:48]=[N+:49]=[N-:50].C1C=CC=CC=1.C(OC(N=NC(OCC)=O)=O)C.N=[N+]=[N-]>C(#N)C>[N:48]([CH:2]1[CH2:6][N:5]([C:7](=[O:24])[CH2:8][P:9]([O:21][CH2:22][CH3:23])([CH2:11][CH2:12][CH2:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:10])[C@H:4]([C:25]([O:27][CH3:28])=[O:26])[CH2:3]1)=[N+:49]=[N-:50]

Participants

7

Reactant 5

HCID 11776Triphenylphosphine2×HCID 24530Hydrazoic acidHCID 220568ethyl N-ethoxycarbonyliminocarbamate2×HCID 70291861Hydrazoic acid benzeneHCID 131712757(S)-4-Hydroxy-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-L-proline, methyl ester

Product 1

HCID 131712758(S)-4-Azido-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-L-proline, methyl ester

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

(S)-4-Hydroxy-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-L-proline, methyl ester (2.0 g), triphenylphosphine (2.57 g), 2.1 N hydrazoic acid/benzene (12 ml, >5 equivalents) and dry acetonitrile are stirred under argon at room temperature for 30 minutes. Diethylazocarboxylate (1.71 g) in acetonitrile (5 ml) is added dropwise over 30 minutes. After 18 hours the reaction is still incomplete (as shown by thin-layer chromatography) and triphenylphosphine (1 equivalent), diethylazocarboxylate (1 equivalent) and 2.1 N hydrazoic acid (6 ml) are added. After 4 hours the reaction is complete. Nitrogen is bubbled through the solution to remove excess hydrazoic acid and the solvent is stripped leaving an oil. The oil is chromatographed on 100 mg of silica gel, eluting first with ethyl acetate and then with 3% methanol/ethyl acetate to give 1.64 g of the title compound.

Workup

  1. waitAfter 4 hours the reaction is complete
  2. customNitrogen is bubbled through the solution
  3. customto remove excess hydrazoic acid
  4. customthe solvent is stripped leaving an oil
  5. customThe oil is chromatographed on 100 mg of silica gel
  6. washeluting first with ethyl acetate

Sources & evidence

ORD record
ord-fce53fada788401696cbf19d8552bdb7
Source dataset
uspto-grants-1983_05
Patent number
US04384123

Reaction notes

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