HCID 14523419, compound → HCID 53722306, compound

HRID 2050664Notes

Reaction equation

HRID 2050664 reaction equation
C(O[C@H]1[C@H]2CN[C@@H]1[C@@H](O2)OC)C1C=CC=CC=1.[CH2:18]([O:25][C@H:26]1[C@H:32]2[CH2:33][N:34]([C:35]([O:37][CH2:38][C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)=[O:36])[C@@H:27]1[C@@H:28]([O:31]2)[O:29][CH3:30])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C(Cl)(Cl)Cl>[CH2:18]([O:25][C@H:26]1[C@H:32]2[CH2:33][N:34]([C:35]([O:37][CH2:38][C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)=[O:36])[C@@H:27]1[CH:28]([O:31]2)[O:29][CH3:30])[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

4

Reactant 2

HCID 14523419HCID 14523419, compoundHCID 14523422HCID 14523422, compound

Product 1

HCID 53722306HCID 53722306, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent3×

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).

Sources & evidence

ORD record
ord-1a5c05666d664e7ea9ac65e2fa385706
Source dataset
uspto-grants-1991_05
Patent number
US05013842

Reaction notes

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