HCID 14523415, compound → HCID 14523418, compound

HRID 2050662Notes

Reaction equation

HRID 2050662 reaction equation
[N:1]([CH2:4][C@H:5]1[O:11][C@H:8]([O:9][CH3:10])[C@H:7](OS(C(F)(F)F)(=O)=O)[C@H:6]1[O:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)=[N+]=[N-]>C(OCC)(=O)C.[Pd]>[CH2:21]([O:20][C@H:6]1[C@H:5]2[CH2:4][NH:1][C@@H:7]1[C@H:8]([O:11]2)[O:9][CH3:10])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

Participants

4

Reactant 1

HCID 14523415HCID 14523415, compound

Product 1

HCID 14523418HCID 14523418, compoundYield 95.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Methyl 5-azido-3-O-benzyl-5-deoxy-2-O-trifluoromethanesulphonyl-α-D-xylofuranoside (12α) (1.60 g, 3.89 mmol) was dissolved in ethyl acetate (30 ml) and stirred under hydrogen at room temperature with 5% palladium on charcoal (200 mg) for four hours. The solution was filtered through celite, concentrated, and purified by flash chromatography (10% ethanol in dichloromethane) to yield methyl 3-O-Benzyl-2,5-dideoxy-2,5-imino-α-D-lyxofuranoside (870 mg, 95%) as a pale brown oil, which rapidly darkened, Rf 0.3 (10% ethanol in dichloromethane); νmax (film) 3420 (NH), 2940, 1450, 1245, 1170, 1025 and 640 cm-1 ; 1H NMR δ 3.14, 3.37 (2H, 2×d, H-5,5', J5,5' 15.0 Hz); 3.79 (1H, s, H-2); 4.29, 4.40 (2H, 2×bs, H-3, H-4); 4.52, 4.70 (2H, 2 x d, CH2Ph, JH,H' 12.4 Hz); 5.88 (1H, s, H-1); 6.23 (1H, bs, NH); 7.30-7.42 (5H, m, H-Ph). 13C NMR δ 49.47 (t, C-5); 55.56 (q, CH3); 59.88 (d, C-2); 72.85 (t, CH2Ph); 74.03, 78.32 (2d, C-3, C-4); 103.38 (d, C-1); 128.19, 128.37, 128.67 (3d, HC-Ph); 136.64 (s, C-Ph). m/z: 236 (M+H+, 100%), 68 (30%), 91 (15%). Methyl 5-azido-3-O-benzyl-5-deoxy-2-O-trifluoromethanesulphonyl-β-D-xylofuranoside (12) (1.57 g, 3.82 mmol) under the same conditions gave methyl 3-O-benzyl-2,5-dideoxy-2,5-imino-β-D-lyxofuranoside (829 mg, 92.5%) after chromatography, as a rapidly darkening oil, Rf 0.4 (10% ethanol in dichloromethane); νmax (film) 3400 (NH), 2910, 1450, 1255, 1115, 1030 and 640 cm-1 ; 1H NMR δ 3.46 (3H, s, CH3); 3.48 (2H, m, H-5); 4.21, (1H, s, H-2); 4.28 (2H, bs, H-3, H-4); 4.55, 4.76 (2H, 2×d, CH2Ph, JH,H' 12.0 Hz); 5.06 (1H, d, H-1, J1,2 1.9 Hz); 6.29 (1H, bs, NH); 7.33-7.38 (5H, m, H-Ph). 13C NMR δ 49.94 (t, C-5); 55.92 (q, CH3); 60.50 (d, C-2); 72.58 (t, CH2Ph); 76.27, 78.84 (2×d, C-3, C-4); 100.50 (d, C-1); 128.34, 128.64, (2×d, HC-Ph); 136.37 (s, C-Ph). m/z: 236 (M+H+, 100%), 68 (40%), 91 (20%).

Workup

  1. filtrationThe solution was filtered through celite,
  2. concentrationconcentrated
  3. custompurified by flash chromatography (10% ethanol in dichloromethane)

Sources & evidence

ORD record
ord-88d74982bac4469787a156111f744d31
Source dataset
uspto-grants-1991_05
Patent number
US05013842

Reaction notes

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