Sulfuric Acid → 2,3,4,6-Tetra-O-benzyl-D-mannopyranose

HRID 522176ノート

反応式

HRID 522176 の反応式
[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]([O:31]C)[O:11][C@@H:10]1[CH2:33][O:34][CH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.OS(O)(=O)=O.C(=O)([O-])[O-].[K+].[K+]>C(O)(=O)C>[CH2:24]([O:23][C@H:13]1[C@@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@H:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C@@H:10]([CH2:33][O:34][CH2:35][C:36]2[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=2)[O:11][CH:12]1[OH:31])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

参加物

5

反応物 3

HCID 1118Sulfuric AcidHCID 11430Potassium CarbonateHCID 10840492Methyl 2,3,4,6-Tetra-O-benzyl-a-D-mannopyranoside

生成物 1

HCID 110169932,3,4,6-Tetra-O-benzyl-D-mannopyranose収率 54.9%

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

反応条件

温度
80 °C

実験手順

To a solution of (2R,3R,4S,5S,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-methoxytetrahydro-2H-pyran (28.0 g, 50.5 mmol, 1.0 equiv) in acetic acid (480 mL), was added 3M H2SO4 (120 mL, aqueous) at 0° C. The reaction was heated at 80° C. for 10 hours, cooled to room temperature, and then neutralized with saturated aqueous potassium carbonate solution. The mixture was then extracted with DCM (3×1000 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The material thus obtained was purified by silica gel chromatography, eluting with 30% EtOAc in petroleum ether, to give (3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-ol as a pale yellow oil (15.0 g, 54%). 1H NMR (300 MHz, DMSO-d6) δ 7.38-7.17 (m, 20H), 6.61 (d, J=4.4 Hz, 1H), 5.14-5.07 (m, 1H), 4.77 (t, J=8.5 Hz, 3H), 4.71-4.38 (m, 6H), 3.80 (dp, J=22.8, 9.1, 8.3 Hz, 3H), 3.68-3.53 (m, 2H). ESI (M+H2O) 558.2; calc for C34H36O6 540.3.

後処理

  1. temperaturecooled to room temperature
  2. extractionThe mixture was then extracted with DCM (3×1000 mL)
  3. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe material thus obtained
  7. customwas purified by silica gel chromatography
  8. washeluting with 30% EtOAc in petroleum ether

出典と根拠

ORDレコード
ord-000bb1af68e64784be6395c2c2aa3d82
出典データセット
uspto-grants-2016_05
特許番号
US09328134B2

反応ノート

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