Dimethylformamide → HCID 117762538, compound

HRID 1474641Notes

Reaction equation

HRID 1474641 reaction equation
[C:1]([O:4][C@H:5]1[C@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@@H:10]([O:16][C:17](=[O:19])[CH3:18])[C@:9]2([C:21]3[CH:26]=[CH:25][C:24]([Cl:27])=[C:23]([CH2:28]Br)[CH:22]=3)[O:20][C@@:6]1([CH2:30][O:31][C:32](=[O:34])[CH3:33])[CH2:7][O:8]2)(=[O:3])[CH3:2].CC1(C)C(C)(C)OB([C:43]2[CH:58]=[CH:57][C:46]([O:47][C:48]3[CH:53]=[CH:52][C:51]([C:54](=[O:56])[CH3:55])=[CH:50][CH:49]=3)=[CH:45][CH:44]=2)O1.C(=O)([O-])[O-].[Na+].[Na+].CN(C=O)C>[Pd].O>[C:1]([O:4][C@H:5]1[C@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@@H:10]([O:16][C:17](=[O:19])[CH3:18])[C@:9]2([C:21]3[CH:26]=[CH:25][C:24]([Cl:27])=[C:23]([CH2:28][C:43]4[CH:44]=[CH:45][C:46]([O:47][C:48]5[CH:53]=[CH:52][C:51]([C:54](=[O:56])[CH3:55])=[CH:50][CH:49]=5)=[CH:57][CH:58]=4)[CH:22]=3)[O:20][C@@:6]1([CH2:30][O:31][C:32](=[O:34])[CH3:33])[CH2:7][O:8]2)(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 86729345HCID 86729345, compound2×HCID 89442771HCID 89442771, compound

Product 1

HCID 117762538HCID 117762538, compoundYield 36.6%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of (1R,2S,3S,4R,55)-1-(acetoxymethyl)-5-(3-(bromomethyl)-4-chlorophenyl)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triyl triacetate (1.0 g, 1.77 mmol, Intermediate 2), 1-(4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy)phenyl)ethanone (899.0 mg, 2.66 mmol), Pd (dppf) Cl2 (72 mg, 0.09 mmol) and sodium carbonate (563.0 mg, 5.31 mmol) under nitrogen atmosphere, was added DMF and H2O (9 mL, 1:1). The reaction mixture was heated at 80° C. for 1 h. After the completion of the reaction, as confirmed by TLC, the solution was cooled to r.t. and filtered through celite. The solvent was evaporated in vacuo and the crude compound was diluted with ethyl acetate (200 mL). The organic layer was washed with water (3×30 mL), separated, dried over Na2SO4 and concentrated in vacuo to afford crude compound which was purified by column chromatography (silica gel, 1:4 EtOAc:Pet ether) to afford the title compound (450 mg, 36.6%) as a white solid.

Workup

  1. customAfter the completion of the reaction
  2. temperaturethe solution was cooled to r.t.
  3. filtrationfiltered through celite
  4. customThe solvent was evaporated in vacuo
  5. additionthe crude compound was diluted with ethyl acetate (200 mL)
  6. washThe organic layer was washed with water (3×30 mL)
  7. customseparated
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated in vacuo
  10. customto afford crude compound which
  11. customwas purified by column chromatography (silica gel, 1:4 EtOAc:Pet ether)

Sources & evidence

ORD record
ord-c0ab9a716b9e493b8e0f81547cef0e20
Source dataset
uspto-grants-2015_04
Patent number
US09018249B2

Reaction notes

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