Triacetoxyperiodinane → 3-[2-(2-Carbazol-9-yl-2-oxo-ethyl)-pentanoylamino]-5-fluoro-4-oxo-pentanoic acid tert-butyl ester

HRID 2422345Notes

Reaction equation

HRID 2422345 reaction equation
C1C2N(C(=O)C[C@@H](CCC)C(O)=O)C3C(=CC=CC=3)C=2C=CC=1.[C:24]([O:28][C:29](=[O:59])[CH2:30][CH:31]([NH:36][C:37](=[O:58])[CH:38]([CH2:42][C:43]([N:45]1[C:57]2[CH:56]=[CH:55][CH:54]=[CH:53][C:52]=2[C:51]2[C:46]1=[CH:47][CH:48]=[CH:49][CH:50]=2)=[O:44])[CH2:39][CH2:40][CH3:41])[CH:32]([OH:35])[CH2:33][F:34])([CH3:27])([CH3:26])[CH3:25].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C1=CC=CC=2)=O>C(Cl)Cl>[C:24]([O:28][C:29](=[O:59])[CH2:30][CH:31]([NH:36][C:37](=[O:58])[CH:38]([CH2:42][C:43]([N:45]1[C:57]2[CH:56]=[CH:55][CH:54]=[CH:53][C:52]=2[C:51]2[C:46]1=[CH:47][CH:48]=[CH:49][CH:50]=2)=[O:44])[CH2:39][CH2:40][CH3:41])[C:32](=[O:35])[CH2:33][F:34])([CH3:25])([CH3:26])[CH3:27]

Participants

5

Reactant 3

HCID 159087TriacetoxyperiodinaneHCID 57418779(2R)-2-(2-carbazol-9-yl-2-oxo-ethyl)-pentanoic acidHCID 668783273-[2-(2-carbazol-9-yl-2-oxo-ethyl)-pentanoylamino]-5-fluoro-4-hydroxy-pentanoic Acid Tert-Butyl Ester

Product 1

HCID 723594993-[2-(2-Carbazol-9-yl-2-oxo-ethyl)-pentanoylamino]-5-fluoro-4-oxo-pentanoic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A stirred solution of [3S/R, 4S/R, (2R)]-3-[2-(2-carbazol-9-yl-2-oxo-ethyl)-pentanoylamino]-5-fluoro-4-hydroxy-pentanoic acid tert-butyl ester (2.51 g, 5.03 mmol) in anhydrous DCM (60 ml) was treated with 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (2.35 g, 5.53 mmol) at 0° C. The resulting mixture was kept at 0° C. for 3 h, diluted with DCM, and then washed sequentially with saturated aqueous sodium thiosulphate, NaHCO3 solution and brine. The organics were dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (25% ethyl acetate in 40/60 hexanes) to afford the sub-title compound as an off white solid (1.437 g, 57%): IR (solid, cm−1) 1722, 1689, 1636, 1531, 1441, 1365, 1279, 1155; 1H NMR (400 MHz, CDCl3) δ 0.85-1.50 (3H, m), 1.35-1.54 (11H, m) 1.55-1.69 (1H, m), 1.78-1.95 (1H, m), 2.67-3.28 (4H, m), 3.60-3.79 (1H, m), 4.80-5.59 (3H, m), 6.89-7.04 (1H, m), 7.33-7.54 (4H, m), 7.98-8.04 (2H, m), 8.15-8.28 (2H, m); 13C (100 MHz, CDCl3) δ 14.12, 14.40, 14.47, 14.60, 20.78, 20.84, 21.47, 28.32, 28.42, 28.48, 29.77, 33.63, 34.58, 34.91, 40.05, 43.05, 43.26, 43.29, 52.60, 53.00, 53.64, 66.90, 66.99, 82.62, 82.69, 85.53, 116.88, 116.94, 120.28, 120.31, 124.27, 127.76, 127.86, 128.69, 128.77, 128.99, 138.80, 171.21, 171.29, 172.21, 172.25, 175.53, 176.03, 203.04, 203.20, 203.30, 203.46; 19F (376 MHz, CDCl3) δ −232.12, −233.24.

Workup

  1. washwashed sequentially with saturated aqueous sodium thiosulphate, NaHCO3 solution and brine
  2. dry with materialThe organics were dried (Na2SO4)
  3. concentrationconcentrated
  4. customThe residue was purified by flash chromatography (25% ethyl acetate in 40/60 hexanes)

Sources & evidence

ORD record
ord-d23e6b8caca249f08fff3908c5f6730f
Source dataset
uspto-grants-2011_06
Patent number
US07960398B2

Reaction notes

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