(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal → 1,2,3,4,6-Penta-O-(3,4,5-tri-O-benzylgalloyl)-b-D-glucopyranose

HRID 508488Notes

Reaction equation

HRID 508488 reaction equation
[O:1]=[CH:2][C@@H:3]([C@H:5]([C@@H:7]([C@@H:9]([CH2:11][OH:12])[OH:10])[OH:8])[OH:6])[OH:4].[CH2:13]([O:20][C:21]1[CH:22]=[C:23]([CH:27]=[C:28]([O:38][CH2:39][C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[C:29]=1[O:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[C:24]([OH:26])=O)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.CCN=C=N[CH2:51][CH2:52][CH2:53]N(C)C.Cl>CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:14]1([CH2:13][O:20][C:21]2[CH:22]=[C:23]([CH:27]=[C:28]([O:38][CH2:39][C:40]3[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=3)[C:29]=2[O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:24]([O:1][C@@H:2]2[O:10][C@H:9]([CH2:11][O:12][C:24](=[O:26])[C:23]3[CH:22]=[C:21]([O:20][CH2:13][C:14]4[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=4)[C:29]([O:30][CH2:31][C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)=[C:28]([O:38][CH2:39][C:51]4[CH:52]=[CH:53][CH:41]=[CH:40][CH:45]=4)[CH:27]=3)[C@@H:7]([O:8][C:24](=[O:26])[C:23]3[CH:27]=[C:28]([O:38][CH2:39][C:40]4[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=4)[C:29]([O:30][CH2:31][C:32]4[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=4)=[C:21]([O:20][CH2:13][C:14]4[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=4)[CH:22]=3)[C@H:5]([O:6][C:24](=[O:26])[C:23]3[CH:27]=[C:28]([O:38][CH2:39][C:40]4[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=4)[C:29]([O:30][CH2:31][C:32]4[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=4)=[C:21]([O:20][CH2:13][C:14]4[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=4)[CH:22]=3)[C@H:3]2[O:4][C:24](=[O:26])[C:23]2[CH:27]=[C:28]([O:38][CH2:39][C:40]3[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=3)[C:29]([O:30][CH2:31][C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)=[C:21]([O:20][CH2:13][C:14]3[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=3)[CH:22]=2)=[O:26])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 107526(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanalHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 111339693,4,5-Tris(benzyloxy)benzoic Acid

Product 1

HCID 161536161,2,3,4,6-Penta-O-(3,4,5-tri-O-benzylgalloyl)-b-D-glucopyranoseYield 9.4%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of 1.17 mmol of D-glucose, 8.57 mmol of 3,4,5-tribenzyloxybenzoic acid, 10.68 mmol of EDC.HCl and 9.84 mmol of DMAP was suspended in 130 mL of CH2Cl2 and was heated at reflux overnight. The cooled reaction mixture was then extracted with 1N HCl (3×), saturated NaHCO3 (2×), and brine (2×), the organic layer was dried over MgSO4, filtered, and concentrated. The resulting residue was purified by column chromatography over silica gel (75:24:1 CH2Cl2:toluene:ethyl acetate) to provide 0.253 g (9%) of product. 1H NMR (CDCl3, 400 MHz) δ 7.45−7.15 (m, 85H), 6.21 (d, J=8.0 Hz, 1H), 6.05 (t, J=10.0 Hz, 1H), 5.84 (dd, J=10.0, 8.0 Hz, 1H), 5.73 (t, J=10.0 Hz, 1H), 5.14−4.92 (m, 30H), 4.76 (m, 1H), 4.44 (m, 1H), 4.35 (m, 1H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. customThe cooled reaction mixture
  4. extractionwas then extracted with 1N HCl (3×), saturated NaHCO3 (2×), and brine (2×)
  5. dry with materialthe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe resulting residue was purified by column chromatography over silica gel (75:24:1 CH2Cl2:toluene:ethyl acetate)

Sources & evidence

ORD record
ord-4b670915377440d7878e059e2a0a663a
Source dataset
uspto-grants-2015_08
Patent number
US09096501B2

Reaction notes

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