Barium Carbonate → 3-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactone

HRID 2050673Notes

Reaction equation

HRID 2050673 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:16]([OH:17])[CH2:15][CH2:14][N:13]([C:18]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[O:19])[C@@H:10]1[CH:11]=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Ba+2].BrBr.S([O-])([O-])(=O)=S.[Na+].[Na+]>O1CCOCC1.O>[CH2:1]([O:8][C@H:9]1[C@H:16]2[CH2:15][CH2:14][N:13]([C:18]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])[C@@H:10]1[C:11]([O:17]2)=[O:12])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 10563Barium CarbonateHCID 24408Bromine2×HCID 24477Sodium ThiosulfateHCID 1317168873-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexose

Product 1

HCID 145234483-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactoneYield 84.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 1,5-imino-1,2,5-trideoxy-D-arabino-hexitol (24) (407 mg, 1.10 mmol) in a 1:3 mixture of water and 1,4-dioxan containing barium carbonate (653 mg, 3.31 mmol), was cooled to 0° C. and treated with bromine (70 μl, 221 mg, 1.37 mmol), then stirred at room temperature for 24 hours. Sodium thiosulphate solution (1M, aqueous) was added until the bromine was removed then the solution acidified with hydrochloric acid (2M, aq, 30 ml) and centrifuged. The supernatent was removed and extracted with ethyl acetate (4×20 ml). The combined organic phase was dried, filtered and evaporated. Purification by flash chromatography gave 3-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactone (342 mg, 84%) as a clear oil, [α]20D -13.7° (c, 1.42 in chloroform); νmax (film) 3030, 2880, 1790 (lactone CO), 1700 (Z CO), 1425, 1260, 1170, 1060, and 700 cm-1 ; 1H NMR δ 1.80-1.93 (1H, m, H-5); 2.28-2.35 (1H, m, H-5'); 3.15-3.20 (1H, m, H-6); 3.93-4.07 (1H, m, H-6'); 4.15, 4.28 (1H, 2×dd, H-3); 4.39-4.61 (2H, m, H-2, H-4); 4.74-4.83 (2H, m, CH2Ph; 5.04-5.20 (3H, m, H-1, CH2 -Z), 7.17-7.35 (10H, m, 2×H-Ph). 13C NMR δ 26.25 (t, C-5); 35.27, 35.49 (2×t, C-6); 65.92, 66.17 (2×d, C-4); 67.38 (t, CH2 -Z); 71.45 (t, CH2Ph); 75.86 (d, C-3); 127.87, 127.98, 128.08, 128.57 (4×d, HC-Ph); 136.78, 137.73 (2×s, C-Ph); 155.15 (s, C=O-Z); 170.34 (s, C-1). m/z (CI NH3): 91 (100%), 324 (M-CO2 +H+, 60%), 385 (M+NH4+, 25%). (Found C, 68.56; H, 5.96; N, 3.51. C21H21NO5 requires C, 68.68; H, 5.76; N, 3.81).

Workup

  1. customwas removed
  2. customThe supernatent was removed
  3. extractionextracted with ethyl acetate (4×20 ml)
  4. customThe combined organic phase was dried
  5. filtrationfiltered
  6. customevaporated
  7. customPurification by flash chromatography

Sources & evidence

ORD record
ord-4d9e375b0cc6485aa41ec3e02c5e9b08
Source dataset
uspto-grants-1991_05
Patent number
US05013842

Reaction notes

Loading…