Acetic Acid → 2-{[3-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)propyl]amino}ethyl 2-(acetylamino)-2-deoxy-beta-D-glucopyranoside

HRID 1488288Notes

Reaction equation

HRID 1488288 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@H:12]([CH3:31])[O:11][C@H:10]1[CH2:32][CH2:33][CH:34]=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O:39][C@H:40]1[C@H:49]([O:50]C(=O)C)[C@@H:48]([CH2:54][O:55]C(=O)C)[O:47][C@@H:42]([O:43][CH2:44][CH2:45][NH2:46])[C@@H:41]1[NH:59][C:60](=[O:62])[CH3:61])(=O)C.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].O(C)[Na]>C(Cl)Cl.CO>[C:60]([NH:59][C@@H:41]1[C@@H:40]([OH:39])[C@H:49]([OH:50])[C@@H:48]([CH2:54][OH:55])[O:47][C@H:42]1[O:43][CH2:44][CH2:45][NH:46][CH2:34][CH2:33][CH2:32][C@@H:10]1[O:11][C@@H:12]([CH3:31])[C@@H:13]([O:23][CH2:24][C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[C@@H:14]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C@@H:9]1[O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)(=[O:62])[CH3:61]

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 5049666Sodium triacetoxyborohydrideHCID 152815833-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)propanalHCID 542114332-aminoethyl 3,4,6-tri-O-acetyl-2-(acetylamino)-2-deoxy-beta-D-glucopyranosideHCID 178418582HCID 178418582, compound

Product 1

HCID 1180056522-{[3-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)propyl]amino}ethyl 2-(acetylamino)-2-deoxy-beta-D-glucopyranoside

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a mixture of 3-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)propanal (800 mg, 1.69 mmol) and 2-aminoethyl 3,4,6-tri-O-acetyl-2-(acetylamino)-2-deoxy-β-D-glucopyranoside (987 mg, 2.53 mmol) in CH2Cl2 (15 mL) was added acetic acid (29 μL, 0.506 mmol) and sodium triacetoxyborohydride (893 mg, 4.21 mmol). After stirring at rt overnight, the reaction mixture was concentrated and the residue was taken up in EtOAc (70 mL), washed with sat'd NaHCO3 (2×100 mL), brine (30 mL), dried over Na2SO4, filtered and concentrated. The residue was taken up in CH3OH (8 mL), to which NaOCH3 (27 mg, 0.506 mmol) was added. After stirring at rt for 2 hr, the resulting mixture was concentrated and the residue was purified by flash chromatography on C18 reverse phase silica gel (120 g), eluting with 5-100% AcCN in water to give the title compound. 1H NMR (CDCl3, 400 MHz) δ 1.30 (d, J=6.6, 3H), 1.50 (m, 1H), 1.60 (m, 1H), 1.68 (m, 1H), 2.02 (s, 3H), 2.64 (m, 2H), 2.81 (m, 2H), 3.39 (m, 1H), 3.57 (m, 2H), 3.69 (m, 1H), 3.78-3.85 (m, 4H), 3.92 (m, 2H), 4.00 (m, 2H), 4.45 (d, J=7.7, 1H), 4.52 (d, J=11.9, 1H), 4.62 (d, J=11.8, 1H), 4.68 (d, J=12.1, 1H), 4.79 (d, J=12.0, 2H), 7.28-7.38 (m, 15H), 7.65 (s, 1H); [M+H/e]+=723.3925.

Workup

  1. concentrationthe reaction mixture was concentrated
  2. washwashed with sat'd NaHCO3 (2×100 mL), brine (30 mL)
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. additionwas added
  7. stirringAfter stirring at rt for 2 hr
  8. concentrationthe resulting mixture was concentrated
  9. customthe residue was purified by flash chromatography on C18 reverse phase silica gel (120 g)
  10. washeluting with 5-100% AcCN in water

Sources & evidence

ORD record
ord-a5a572e76bc743f19bd50a147cdea512
Source dataset
uspto-grants-2016_08
Patent number
US09427475B2

Reaction notes

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