Hydrochloric Acid → 2-Methyl-4-(4-nitro-benzoyloxy)-pyrrolidine-1-carboxylic Acid T-butyl Ester

HRID 1454265Notes

Reaction equation

HRID 1454265 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]([OH:13])[CH2:10][CH:9]1[CH3:14])=[O:7])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+:34]([C:37]1[CH:45]=[CH:44][C:40]([C:41](O)=[O:42])=[CH:39][CH:38]=1)([O-:36])=[O:35].CCOC(/N=N/C(OCC)=O)=O.Cl>C1COCC1.CCCCCC.C(OCC)(=O)C>[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]([O:13][C:41](=[O:42])[C:40]2[CH:39]=[CH:38][C:37]([N+:34]([O-:36])=[O:35])=[CH:45][CH:44]=2)[CH2:10][CH:9]1[CH3:14])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 14117009tert-Butyl 4-hydroxy-2-methylpyrrolidine-1-carboxylate

Product 1

HCID 685656492-Methyl-4-(4-nitro-benzoyloxy)-pyrrolidine-1-carboxylic Acid T-butyl Ester

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

The 4-hydroxy-2-methyl-pyrrolidine-1-carboxylic acid t-butyl ester (300.00 mg, 1.49 mmol) and triphenyl phosphine (512.54, 1.95 mmol) were dissolved in anhydrous THF and added to a mixture of para-nitrobenzoic acid (249.00 mg, 1.49 mmol) and DEAD (268.00 mg, 1.54 mmol, 0.24 mL) in anhydrous THF at 0EC under argon. The mixture was stirred for 1 h at 0EC. After 1 h the TLC indicated no starting material remained and the reaction mixture was poured into a 1N HCl solution and the aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with water and brine then dried over MgSO4. The solution was filtered and the solvent removed under reduced pressure. The product was isolated by flash chromatography. (2:1 hexane-ethyl acetate) Yield 391.54 mg. 1H NMR (CDCl3, 300 MHz): δ 1.39 (d, J=9 Hz, 3H), 1.49 (s, 9H), 1.99 (d, J=15 Hz, 1H), 2.24-2.33 (m, 1H), 3.62-3.71 (m, 1H), 3.82 (dd, J=7, 12 Hz, 1H), 4.13 (bs, 1H), 5.52-5.56 (m, 1H), 8.20-8.35 (m, A2B2), 4H).

Workup

  1. waitAfter 1 h the TLC indicated
  2. extractionthe aqueous layer was extracted three times with ethyl acetate
  3. washThe combined organic layers were washed with water and brine
  4. dry with materialthen dried over MgSO4
  5. filtrationThe solution was filtered
  6. customthe solvent removed under reduced pressure
  7. customThe product was isolated by flash chromatography

Sources & evidence

ORD record
ord-859cf076a1fa43719f8aadb4338f19e1
Source dataset
uspto-grants-2009_01
Patent number
US07479495B2

Reaction notes

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