3-Buten-1-ol → 4-{4-[(1E)-4-hydroxybut-1-en-1-yl]-2-methylbenzyl}-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside

HRID 1625936ノート

反応式

HRID 1625936 の反応式
[CH2:1]([OH:5])[CH2:2][CH:3]=[CH2:4].[C:6]([O:9][C@@H:10]1[C@@H:33]([O:34][C:35](=[O:37])[CH3:36])[C@H:32]([O:38][C:39](=[O:41])[CH3:40])[C@@H:31]([CH2:42][O:43][C:44](=[O:46])[CH3:45])[O:30][C@H:11]1[O:12][C:13]1[C:17]([CH2:18][C:19]2[CH:24]=[CH:23][C:22](Br)=[CH:21][C:20]=2[CH3:26])=[C:16]([CH:27]([CH3:29])[CH3:28])[NH:15][N:14]=1)(=[O:8])[CH3:7].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)C.C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:6]([O:9][C@@H:10]1[C@@H:33]([O:34][C:35](=[O:37])[CH3:36])[C@H:32]([O:38][C:39](=[O:41])[CH3:40])[C@@H:31]([CH2:42][O:43][C:44](=[O:46])[CH3:45])[O:30][C@H:11]1[O:12][C:13]1[C:17]([CH2:18][C:19]2[CH:24]=[CH:23][C:22](/[CH:4]=[CH:3]/[CH2:2][CH2:1][OH:5])=[CH:21][C:20]=2[CH3:26])=[C:16]([CH:27]([CH3:29])[CH3:28])[NH:15][N:14]=1)(=[O:8])[CH3:7]

参加物

7

反応物 3

HCID 693893-Buten-1-olHCID 80271Tri-o-tolylphosphineHCID 685376803-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyloxy)-4-[(4-bromo-2-methyl-phenyl)methyl]-5-isopropyl-1H-pyrazole

生成物 1

HCID 867151534-{4-[(1E)-4-hydroxybut-1-en-1-yl]-2-methylbenzyl}-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside収率 50.6%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 6342Acetonitrile溶媒HCID 8471Triethylamine溶媒

反応条件

温度
90 °C

実験手順

Add 3-buten-1-ol (6.1 mL, 70 mmol) to a solution of 4-(4-bromo-2-methylbenzyl)-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside (15 g, 23.5 mmol) in acetonitrile (200 mL) and triethylamine (50 mL). Degas the solution with nitrogen over 10 minutes. Add tri-o-tolylphosphine (1.43 g, 4.7 mmol) and palladium acetate (526 mg, 2.35 mmol). After refluxing at 90° C. for 2 hours, cool and concentrate to remove the solvent under reduced pressure. Purify the resulting residue by flash chromatography (silica gel, gradient ethyl acetate/hexanes from 20-80% over 20 min, 330 g column) to provide the title compound (7.5 g, 11.9 mmol). MS (m/z): 631.2 (M+1), 629.2 (M−1).

後処理

  1. customDegas the solution with nitrogen over 10 minutes
  2. temperaturecool
  3. concentrationconcentrate
  4. customto remove the solvent under reduced pressure
  5. customPurify the resulting residue by flash chromatography (silica gel, gradient ethyl acetate/hexanes from 20-80% over 20 min, 330 g column)

出典と根拠

ORDレコード
ord-a20fa3672e6146649b79c7b3eed5238c
出典データセット
uspto-grants-2014_07
特許番号
US08785404B2

反応ノート

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