Dimethylformamide → HCID 123846402, compound

HRID 595188Notes

Reaction equation

HRID 595188 reaction equation
[CH3:1][C:2]1([CH3:14])[C:6]([CH3:8])([CH3:7])[O:5][B:4]([C:9]2[CH:10]=[N:11][NH:12][CH:13]=2)[O:3]1.[CH3:15][C:16]1([CH3:30])[CH2:21][CH:20](OS(C)(=O)=O)[CH2:19][CH2:18][CH:17]1[C:27]([O-:29])=[O:28].[C:31](=O)([O-])[O-].[Cs+].[Cs+].CN(C=O)C>C(OCC)C>[CH3:15][C:16]1([CH3:30])[CH2:21][CH:20]([N:12]2[CH:13]=[C:9]([B:4]3[O:5][C:6]([CH3:7])([CH3:8])[C:2]([CH3:14])([CH3:1])[O:3]3)[CH:10]=[N:11]2)[CH2:19][CH2:18][CH:17]1[C:27]([O:29][CH3:31])=[O:28]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 27740104-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 131734571HCID 131734571, compound

Product 1

HCID 123846402HCID 123846402, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
90 °C

Procedure

4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (700 mg, 3.61 mmol), 2,2-dimethyl-4-[(methylsulfonyl)oxy]cyclohexanecarboxylate (1.50 g, 3.97 mmol), and cesium carbonate (1.29 g, 3.97 mmol) were added to an oven-dried flask. DMF (12 mL) was added and the mixture was stirred at 90° C. for 22 hours. The mixture was cooled to room temperature, diluted with diethyl ether, washed with water (3×50 mL), and then brine. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (10 to 80% EtOAc/hexanes) to afford racemic methyl 2,2-dimethyl-4-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl]cyclohexanecarboxylate. 1H NMR (500 MHz, DMSO-d6) δ 7.91 (s, 1H), 7.54 (s, 1H), 4.10 (q, J=7.3 Hz, 1H), 3.54 (s, 3H), 2.20-1.98 (m, 1H), 1.83-1.65 (m, 2H), 1.64-1.49 (m, 2H), 1.43-1.38 (m, 1H), 1.34-1.31 (m, 1H), 1.22 (s, 12H), 0.90 (s, 6H).

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. washwashed with water (3×50 mL)
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by column chromatography on silica gel (10 to 80% EtOAc/hexanes)

Sources & evidence

ORD record
ord-8a09895df0cb4f04b39143a0643a10df
Source dataset
uspto-grants-2016_01
Patent number
US09242984B2

Reaction notes

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