Sodium hydride → (1S,3R,4R,7S)-7-Benzyloxy-1-benzyloxymethyl-3-methoxy-2,5-dioxabicyclo[2.2.1]heptane

HRID 2100288ノート

反応式

HRID 2100288 の反応式
[CH2:1]([O:8][C@@H:9]1[C@@:15]([CH2:25][O:26]S(C)(=O)=O)([CH2:16][O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[O:14][C@H:11]([O:12][CH3:13])[C@@H:10]1O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].[Na+]>CN(C=O)C>[CH2:1]([O:8][C@H:9]1[C@H:10]2[O:26][CH2:25][C@:15]1([CH2:16][O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[O:14][C@H:11]2[O:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

4

反応物 2

HCID 24758Sodium hydrideHCID 20610801Methyl 3,5-di-O-benzyl-4-C-methanesulfonyloxymethyl-alpha-D-ribofuranoside

生成物 1

HCID 56975532(1S,3R,4R,7S)-7-Benzyloxy-1-benzyloxymethyl-3-methoxy-2,5-dioxabicyclo[2.2.1]heptane

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

A solution of 201 (3.32 g, 7.34 mmol) in anhydrous DMF (25 mL) was stirred at 0° C. and a 60% oil dispersion of sodium hydride (700 mg, 16.9 mmol) was added. The mixture was stirred at room temperature for 90 min, quenched with water (300 mL) and extracted with diethyl ether (2×300 mL). The combined extract was washed with water (200 mL) and dried (MgSO4). The solvent was removed under reduced pressure and the residue was purified by chromatography over silica gel with dichloromethane as eluent to give the two products 202 and 203 as clear oils (1.571 g, 60% and 0.777 g, 30% respectively). (1S,3R,4R,7S)-7-Benzyloxy-1-benzyloxymethyl-3-methoxy-2,5-dioxabicyclo[2.2.1]heptane (202). 1H NMR (CDCl3): δ 7.36-7.26 (10 H, m, Bn), 4.81 (1 H, s, H-1), 4.65 (1 H, d, J 11.9 Hz, Bn), 4.61 (2 H, s, Bn), 4.56 (1 H, d, J 11.9 Hz, Bn), 4.11 (1 H, s, H-2), 4.09 (1 H, s, H-3), 4.01 (1 H, d, J 7.5 Hz, H-5′), 3.80-3.77 (3 H, m, H-5′, H-5), 3.39 (3 H, s, OCH3); 13C NMR (CDCl3): δ 138.05, 137.36, 128.47, 128.44, 127.88, 127.73, 127.63 (Bn), 104.97 (C-1), 85.13 (C-4), 79.16 (C-3), 77.18 (C-2), 73.64 (Bn), 72.26, 72.10 (Bn, C-5′), 66.50 (C-5), 55.34 (OCH3); MS FAB: 379 (M+Na, 28%). Found: C, 70.55; H, 6.97; C21H24O5 requires C, 70.77; H, 6.79%. (7S,3R,4R,7S)-7-Benzyloxy-1-benzyloxymethyl-3-methoxy-2,5-dioxabicyclo[2.2.1]heptane (203). 1H NMR (CDCl3): δ 7.36-7.26 (10 H, m, Bn), 5.00 (1 H, s, H-1), 4.67-4.54 (4 H, m, Bn), 4.18 (1 H, s, H-2), 3.99 (1 H, s, H-3), 3.99-3.90 (2 H, m, H-5′), 3.75-3.68 (2 H, m, H-5), 3.49 (3 H, s, OCH3); 13C NMR (CDCl3): δ 137.83, 137.53, 128.51, 128.48, 127.96, 127.82, 127.71, 127.62 (Bn), 104.05 (C-1), 88.44 (C-4), 79.54 (C-3), 77.16 (C-2), 73.68 (Bn), 72.61 (C-5′), 72.24 (Bn), 65.73 (C-5), 56.20 (OCH3); MS FAB: 379 (M+Na, 100%).

後処理

  1. customquenched with water (300 mL)
  2. extractionextracted with diethyl ether (2×300 mL)
  3. extractionThe combined extract
  4. washwas washed with water (200 mL)
  5. dry with materialdried (MgSO4)
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was purified by chromatography over silica gel with dichloromethane as eluent

出典と根拠

ORDレコード
ord-ab75b7472b2a44bb9875d4477ae3c301
出典データセット
uspto-grants-2009_08
特許番号
US07572582B2

反応ノート

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