Dimethylformamide → 1-chloro-4-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranos1-yl)-2-(4-methoxymethylethynyl-benzyl)-benzene

HRID 2246493Notes

Reaction equation

HRID 2246493 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C@:8]2([O:26][C@H:25]([CH2:27][O:28][C:29](=[O:31])[CH3:30])[C@@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:10]2[O:11][C:12](=[O:14])[CH3:13])[OH:9])=[CH:4][C:3]=1[CH2:32]C1C=CC(OS(C(F)(F)F)(=O)=O)=CC=1.C(N([CH2:52][CH3:53])CC)C.CN(C)[CH:56]=[O:57].[CH2:59](OC)[C:60]#[CH:61]>C(OCC)(=O)C.[Cu](I)I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C@:8]2([O:26][C@H:25]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[C@@H:27]([O:28][C:29](=[O:31])[CH3:30])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:10]2[O:11][C:12](=[O:14])[CH3:13])[OH:9])=[CH:4][C:3]=1[CH:32]([C:52]#[CH:53])[C:60]1[CH:61]=[CH:4][C:3]([CH2:32][O:57][CH3:56])=[CH:2][CH:59]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 693933-MethoxypropyneHCID 866059781-chloro-4-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranos-1-yl)-2-(4-trifluoromethylsulfonyloxy-benzyl)-benzene

Product 1

HCID 866059771-chloro-4-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranos1-yl)-2-(4-methoxymethylethynyl-benzyl)-benzene

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

1 g 1-chloro-4-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranos-1-yl)-2-[4-(trifluoromethylsulfonyloxy)-benzyl]-benzene, 2 mL triethylamine and 3 mL dimethylformamide are placed in a flask under argon atmosphere. 56 mg copper iodide, 103 mg bis-(triphenylphosphine)-palladium dichloride and finally 0.31 g methyl propargyl ether are added. The flask is tightly sealed and the mixture is stirred at 65° C. for 30 h. Then the reaction mixture is diluted with ethyl acetate and washed with 1 M hydrochloric acid. The organic phase is dried over magnesium sulfate and the solvent is removed under reduced pressure. The residue is chromatographed on silica gel (cyclohexane/ethyl acetate 4:1->2:1).

Workup

  1. customThe flask is tightly sealed
  2. washwashed with 1 M hydrochloric acid
  3. dry with materialThe organic phase is dried over magnesium sulfate
  4. customthe solvent is removed under reduced pressure
  5. customThe residue is chromatographed on silica gel (cyclohexane/ethyl acetate 4:1->2:1)

Sources & evidence

ORD record
ord-65df3f8a4c1240f09edab60a12f50126
Source dataset
uspto-grants-2010_03
Patent number
US07687469B2

Reaction notes

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