Benzyl chloroformate → HCID 14523421, compound

HRID 2050663Notes

Reaction equation

HRID 2050663 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:15]2[CH2:16][NH:17][C@@H:10]1[C@H:11]([O:14]2)[O:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)(O)[O-].[Na+].Cl[C:24]([O:26][CH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:25]>CCOCC>[CH2:1]([O:8][C@H:9]1[C@H:15]2[CH2:16][N:17]([C:24]([O:26][CH2:27][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)=[O:25])[C@@H:10]1[C@H:11]([O:14]2)[O:12][CH3:13])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 10387Benzyl chloroformateHCID 516892Sodium BicarbonateHCID 14523418HCID 14523418, compound

Product 1

HCID 14523421HCID 14523421, compoundYield 76.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Methyl 3-O-benzyl-2,5-dideoxy-2,5-imino-α-D-lyxofuranoside (13α) (870 mg, 3.70 mmol) was stirred with a 3:2 mixture of ether and saturated aqueous sodium bicarbonate (60 ml). Benzyl chloroformate (1.57 ml, 11.1 mmol) was added to the mixture which was stirred at room temperature for 12 hours. The ether layer was separated and the aqueous phase further extracted with ether (4×25 ml). The combined extracts were dried, filtered and the solvent removed. Purification by flash chromatography (ether-hexane 1:10-1:3) afforded methyl 3-O-benzyl-N-benzyloxycarbonyl-2,5-dideoxy-2,5-imino-α-D-lyxofuranoside (1.04 g, 76%) as a white crystalline solid, m.p. 74°-75° C., Rf 0.2 (ether-hexane 1:3); [α]20D +12.0° (c, 0.98 in chloroform); νmax (chloroform) 2940, 1695 (C=O), 1420, 1260, 1230, 1090 and 750 cm-1 ; 1H NMR δ 3.38, 3.41 (3H, 2× s, CH3); 3.3-3.7 (2H, m, 5,5'-H); 4.05-4.90 (5H, m, H-3, H-2, H-4, CH2Ph); 5.12-5.20 (3H, m, H-1, CH2 -Z); 7.2-7.4 (10H, m, 2×H-Ph). 13C NMR δ 50.71 (t, C-5); 55.15, 55.33 (2×q, Me); 59.63, 60.17 (2×d, C-2); 66.95, 67.08 (2×t, CH2 -Z); 72.28 (t, CH2Ph); 75.09, 75.49, 77.93, 78.48 (4×d, C-3, C-4); 105.67, 105.90 (d, C-1); 127.83, 127.92, 128.15, 128.64 (4×d, HC-Ph); 136.68, 137.46 (2×s, C-Ph); 155.68, 155.81 (2×s, C=O). m/z: 91 (100%), 108 (25%), 158 (20%), 370 (M+H+, 10%). (Found C, 67.98; H, 6.39; N, 3.60. C21H23NO5 requires C, 68.28; H, 6.28; N, 3.79). Methyl 3-O-benzyl-2,5-dideoxy-2,5-imino-β-D-lyxofuranoside (13β) (829 mg, 3.53 mmol) was treated likewise giving methyl 3-O-benzyl-N-benzyloxycarbonyl-2,5-dideoxy-2,5-imino-β-D-lyxofuranoside (1.18 g, 90%) as a clear oil, Rf 0.35 (ether-hexane 1:3); [α]20D -75.2° (c, 0.83 in chloroform); νmax (film) 2930, 1705 (C=O), 1425, 1275, 1255, 1105 and 750 cm-1 ; 1H NMR δ 3.36, 3.42 (3H, 2×s, CH3); 3.50 (1H, 2×d 5-H); 3.67 (1H, 2×d, H-5'); 4.02-4.06 (1H, m, H-3); 4.29 (1H, bs, H-2); 4.49, 4.54 (1H, bs and dd, H-4); 4.52-4.65 (2H, m, CH2Ph); 5.0-5.2 (2H, 2×dd, CH2Ph); 5.21 (1H, s, H-1); 7.28-7.38 (10H, m, H-Ph). 13C NMR δ 50.02 (t, C-5); 55.70, 55.89 (2×q, Me); 60.17, 59.52 (2×d, C-2); 66.79 (t, CH2 -Z); 72.00, 72.10 (t, CH2Ph); 77.56, 78.08, 78.52, 79.18 (4×d, C-3, C-4); 104.71, 105.11 (2×d, C-1); 128.79, 127.96, 128.33, 128.61, 128.78 (5×d, HC-Ph); 137.09, 137.22 (2×s, C-Ph); 156.20, 156.45 (2×s, C=O). m/z: 91 (100%), 370 (M+H+, 60%), 202 (30%). (Found C, 68.08; H, 6.39; N, 3.40. C21H 23 NO5 requires C, 68.28; H, 6.28; N, 3.79).

Workup

  1. customThe ether layer was separated
  2. extractionthe aqueous phase further extracted with ether (4×25 ml)
  3. customThe combined extracts were dried
  4. filtrationfiltered
  5. customthe solvent removed
  6. customPurification by flash chromatography (ether-hexane 1:10-1:3)

Sources & evidence

ORD record
ord-990295beebf34ea1b5b09a0cb4f849df
Source dataset
uspto-grants-1991_05
Patent number
US05013842

Reaction notes

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