Triphenylphosphine → bis[(4-nitrophenyl)methyl] (2S,4S)-4-[(Z)-[1-[(2-methylpropan-2-yl)oxy]-1,3-dioxobutan-2-ylidene]amino]oxypyrrolidine-1,2-dicarboxylate

HRID 1194942Notes

Reaction equation

HRID 1194942 reaction equation
[OH:1][C@H:2]1[CH2:6][N:5]([C:7]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=2)=[O:8])[C@H:4]([C:20]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=2)=[O:21])[CH2:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC)=O)=NC(OC)=O.O/[N:63]=[C:64](/[C:72](=[O:74])[CH3:73])\[C:65]([O:67][C:68]([CH3:71])([CH3:70])[CH3:69])=[O:66]>O1CCCC1>[O:74]=[C:72]([CH3:73])/[C:64](=[N:63]/[O:1][C@@H:2]1[CH2:6][N:5]([C:7]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=2)=[O:8])[C@H:4]([C:20]([O:22][CH2:23][C:24]2[CH:25]=[CH:26][C:27]([N+:30]([O-:32])=[O:31])=[CH:28][CH:29]=2)=[O:21])[CH2:3]1)/[C:65]([O:67][C:68]([CH3:70])([CH3:69])[CH3:71])=[O:66]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 351621Azodicarboxylic acid dimethyl esterHCID 136446194-Nitrobenzyl (2S,4R)-4-hydroxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine-2-carboxylateHCID 178468383HCID 178468383, compound

Product 1

HCID 140352850bis[(4-nitrophenyl)methyl] (2S,4S)-4-[(Z)-[1-[(2-methylpropan-2-yl)oxy]-1,3-dioxobutan-2-ylidene]amino]oxypyrrolidine-1,2-dicarboxylateYield 55.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

4-Nitrobenzyl (2S,4R)-4-hydroxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine-2-carboxylate (3.24 g, 7.28 mmol) and triphenylphosphine (2.29 g, 8.7 mmol) in dry tetrahydrofuran (60 ml) under argon were treated with dimethyl azodicarboxylate (1.28 g, 8.7 mmol) in dry tetrahydrofuran (5 ml). After 5 min tert-butyl (Z)-2-hydroxyimino-3-oxobutyrate (2.59 g, 8.7 mmol) in dry tetrahydrofuran (10 ml) was added and the mixture was stirred under an argon atmosphere for 18 h. The tetrahydrofuran was removed and the residue taken up in ethyl acetate (150 ml) and washed with water containing a trace of acetone (100 ml,×6). The ethyl acetate layer was dried (MgSO4) and evaporated under reduced pressure. The residue was chromatographed on silica gel, eluting with ethyl acetate/hexane mixture to give the title compound (2.49 g, 55%) as a mixture of two conformers/rotamers; νmax (CH2Cl2) 1735, 1710, 1605, 1525, and 1350 cm-1 ; δH (250 MHz, CDCl3) 1.52 (9H, s), 2.31 (3H, s), 2.40-2.80 (2H, m), 3.75-4.0 (2H, m), 4.66 (1H, approx dt, J ca 9.3, 1.5 Hz), 4.94-5.05 (1H, m), 5.1-5.4 (4H, m), 7.35-7.55 (4H, m), and 8.05-8.25 (4H, m).

Workup

  1. customThe tetrahydrofuran was removed
  2. washwashed with water containing a trace of acetone (100 ml,×6)
  3. dry with materialThe ethyl acetate layer was dried (MgSO4)
  4. customevaporated under reduced pressure
  5. customThe residue was chromatographed on silica gel
  6. washeluting with ethyl acetate/hexane mixture

Sources & evidence

ORD record
ord-cb15d9ba2fe64bd1bf7e43bb62311713
Source dataset
uspto-grants-1989_03
Patent number
US04816452

Reaction notes

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