Triacetoxyperiodinane → 5-Fluoro-3-{2-[(1H-imidazole-2-carbonyl)-amino]-propionylamino}-4-oxo-pentanoic acid tert-butyl ester

HRID 2422340Notes

Reaction equation

HRID 2422340 reaction equation
C(OC(=O)[C@@H](NC(C1NC=CN=1)=O)C)(C)(C)C.[C:18]([O:22][C:23](=[O:43])[CH2:24][CH:25]([NH:30][C:31](=[O:42])[CH:32]([NH:34][C:35]([C:37]1[NH:38][CH:39]=[CH:40][N:41]=1)=[O:36])[CH3:33])[CH:26]([OH:29])[CH2:27][F:28])([CH3:21])([CH3:20])[CH3:19].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C1=CC=CC=2)=O>ClCCl>[C:18]([O:22][C:23](=[O:43])[CH2:24][CH:25]([NH:30][C:31](=[O:42])[CH:32]([NH:34][C:35]([C:37]1[NH:38][CH:39]=[CH:40][N:41]=1)=[O:36])[CH3:33])[C:26](=[O:29])[CH2:27][F:28])([CH3:19])([CH3:20])[CH3:21]

Participants

5

Reactant 3

HCID 159087Triacetoxyperiodinane2×HCID 57462011HCID 57462011, compoundHCID 670587205-Fluoro-4-hydroxy-3-{2-[(1H-imidazole-2-carbonyl)-amino]-propionylamino}-pentanoic acid tert-butyl ester

Product 1

HCID 101096955-Fluoro-3-{2-[(1H-imidazole-2-carbonyl)-amino]-propionylamino}-4-oxo-pentanoic acid tert-butyl esterYield 84.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of [3S/R, (2S)]-5-fluoro-4-hydroxy-3-{2-[(1H-imidazole-2-carbonyl)-amino]-propionylamino}-pentanoic acid tert-butyl ester (0.381 g) in dichloromethane was cooled to 0° C. before addition of 1,1,1 triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (0.476 g). The mixture was stirred at room temperature for 2 h before addition of an additional portion of 1,1,1 triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (0.05 g) and reaction mixture was then stirred for 90 min before being concentrated at reduced pressure. The residue was dissolved in ethyl acetate and washed with a 1:1 mixture of aqueous NaHSO4 and aqueous Na2S2O3. The organic layer was collected, dried (MgSO4) and concentrated. The residue was purified by flash chromatography (5% methanol in dichloromethane) to give the sub-title compound as a colourless foam (319 mg, 84%): 1H NMR 400 MHz CDCl3 1.37+1.43 (9H, 2×s), 1.54 (3H, m), 2.85 (1H, m), 3.03 (1H, m), 4.85-5.30 (4H, m), 7.18 (2H, d, J 16), 7.90 (1H, m), 7.98 (1H, m), 11.37+11.45 (1H, 2×s); 19F NMR 376 MHz CDCl3 −231.85 (t, J 48), −232.12 (t, J 48).

Workup

  1. concentrationbefore being concentrated at reduced pressure
  2. dissolutionThe residue was dissolved in ethyl acetate
  3. washwashed with a 1:1 mixture of aqueous NaHSO4 and aqueous Na2S2O3
  4. customThe organic layer was collected
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography (5% methanol in dichloromethane)

Sources & evidence

ORD record
ord-0758a33419de4158bd5a282238b2918d
Source dataset
uspto-grants-2011_06
Patent number
US07960398B2

Reaction notes

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