Trifluoroacetic acid → 3-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexose

HRID 2050670Notes

Reaction equation

HRID 2050670 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:15]2[CH2:16][CH2:17][NH:18][C@@H:10]1[C@@H:11]([O:14]2)[O:12]C)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.FC(F)(F)[C:21]([OH:23])=[O:22]>O>[CH2:1]([O:8][C@H:9]1[C@H:15]([OH:14])[CH2:16][CH2:17][N:18]([C:21]([O:23][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[O:22])[C@@H:10]1[CH:11]=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 14523439methyl 3-O-benzyl-2,6-imino-2,5,6-trideoxy-beta-D-lyxo-hexofuranoside

Product 1

HCID 1317168873-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexoseYield 87%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of methyl 3-O-benzyl-2,6-imino-2,5,6-trideoxy-β-D-lyxo-hexofuranoside (23β) (762 mg, 2.06 mmol) in a 1:1 mixture of trifluoroacetic acid and water (20 ml) was stirred at room temperature for 20 minutes. The solvents were removed in vacuo and the crude material purified by flash chromatography (ethyl acetate-hexane 1:2) to give 3-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexose (640 mg, 87%) as a clear oil, [α]20D -17.2° (c, 0.73 in chloroform); νmax (film) 3400 (OH), 2920, 1690 (C=O), 1410, 1345 and 1060 cm-1 ; 1H NMR δ 1.50-1.71 (1H, m, H-5); 1.80 (1H, bs, OH); 2.02-2.20 (1H, m, H-5'); 3.08-3.27 (1H, m, H-6); 3.94-4.20 (2H, m, 6-H, H-3); 4.25-4.85 (4H, m, H-2, H-4, CH2 -Ph); 5.05-5.18 (2H, m, CH2 -Z); 5.50, 5.53 (0.75H, 2×s, H-1-hemiacetal); 7.20-7.40 (10H, m, 2×H-Ph); 9.68 (0.25H, s, H-1-aldehyde). 13C NMR δ 24.17 (t, C-5); 38.10 (t, C-6); 57.26, 57.77 (2×d, C-2); 67.30, 67.48, 67.58 (3×t, CH2 -Z); 71.38, 71.84, 72.12 (3×t, CH2Ph); 74.00, 74.63, 74.76 (3×d, C-3, C-4); 98.72, 98.88, 198.17 (3×d, C-1); 127.35, 127.58, 127.85, 128.01, 128.23, 128.63 (6×d, HC-Ph); 136.51, 136.62, 136.73, 137.46, 155.60 (s, C=O-Z); 137.74, 137.88 (6×s, C-Ph). m/z: 91 (100%), 262 (20%), 370 (M+H+, 15%). (Found C, 68.68; H, 6.40; N, 3.71. C21H23NO5 requires C, 68.28; H, 6.28; N, 3.79).

Workup

  1. customThe solvents were removed in vacuo
  2. customthe crude material purified by flash chromatography (ethyl acetate-hexane 1:2)

Sources & evidence

ORD record
ord-a78277bd37c74358849646f6dbe02caa
Source dataset
uspto-grants-1991_05
Patent number
US05013842

Reaction notes

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