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-benzoyl-beta-D-glucopyranoside

HRID 931672Notes

Reaction equation

HRID 931672 reaction equation
[CH2:1]([OH:5])[CH2:2][CH:3]=[CH2:4].[C:6]([O:14][C@@H:15]1[C@@H:38]([O:39][C:40](=[O:47])[C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C@H:37]([O:48][C:49](=[O:56])[C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)[C@@H:36]([CH2:57][O:58][C:59](=[O:66])[C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)[O:35][C@H:16]1[O:17][C:18]1[C:22]([CH2:23][C:24]2[CH:29]=[CH:28][C:27](Br)=[CH:26][C:25]=2[CH3:31])=[C:21]([CH:32]([CH3:34])[CH3:33])[NH:20][N:19]=1)(=[O:13])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.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:14][C@@H:15]1[C@@H:38]([O:39][C:40](=[O:47])[C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C@H:37]([O:48][C:49](=[O:56])[C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)[C@@H:36]([CH2:57][O:58][C:59](=[O:66])[C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)[O:35][C@H:16]1[O:17][C:18]1[C:22]([CH2:23][C:24]2[CH:29]=[CH:28][C:27](/[CH:4]=[CH:3]/[CH2:2][CH2:1][OH:5])=[CH:26][C:25]=2[CH3:31])=[C:21]([CH:32]([CH3:34])[CH3:33])[NH:20][N:19]=1)(=[O:13])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

7

Reactant 3

HCID 693893-Buten-1-olHCID 80271Tri-o-tolylphosphineHCID 867208784-(4-bromo-2-methylbenzyl)-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-benzoyl-beta-D-glucopyranoside

Product 1

HCID 867208804-{4-[(1E)-4-hydroxybut-1-en-1-yl]-2-methylbenzyl}-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-benzoyl-beta-D-glucopyranosideYield 70.6%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
90 °C

Procedure

Add 3-buten-1-ol (0.58 mL, 6.8 mmol) to a solution of 4-(4-bromo-2-methylbenzyl)-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-benzoyl-beta-D-glucopyranoside (3 g, 3.4 mmol) in acetonitrile (30 mL) and triethylamine (20 mL). Degas the solution with nitrogen over 10 minutes. Add tri-o-tolylphosphine (205 mg, 0.67 mmol) and palladium acetate (76 mg, 0.34 mmol). Reflux at 90° C. for 2 hours. Cool to room temperature and concentrate to remove the solvent under the reduced pressure. Purify the residue by flash chromatography to yield the title compound (2.1 g, 2.4 mmol). MS (m/z): 878.4 (M+1).

Workup

  1. customDegas the solution with nitrogen over 10 minutes
  2. temperatureCool to room temperature
  3. concentrationconcentrate
  4. customto remove the solvent under the reduced pressure
  5. customPurify the residue by flash chromatography

Sources & evidence

ORD record
ord-7407444acdb54ce891ade3a235d73ec4
Source dataset
uspto-grants-2016_03
Patent number
US09296775B2

Reaction notes

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