Dimethylformamide → HCID 59316747, compound

HRID 2189805Notes

Reaction equation

HRID 2189805 reaction equation
Br[C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]=[N:5][N:6]2[CH2:11][CH2:12][C:13]([CH3:20])([CH3:19])[C:14]([O:16][CH2:17][CH3:18])=[O:15].[CH3:21][N:22](C=O)C>CCOC(C)=O.[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:21]([C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]=[N:5][N:6]2[CH2:11][CH2:12][C:13]([CH3:20])([CH3:19])[C:14]([O:16][CH2:17][CH3:18])=[O:15])#[N:22]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 59316726HCID 59316726, compound

Product 1

HCID 59316747HCID 59316747, compoundYield 36%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of ethyl 4-(4-bromo-1H-indazol-1-yl)-2,2-dimethylbutanoate (D112) (600 mg, 1.77 mmol) and Zn(CN)2 (207 mg, 1.77 mmol) in DMF (5 ml) at room temperature was added Pd(PPh3)4 (204 mg, 0.18 mmol) and the resulting mixture was stirred at 100° C. over the weekend, heated for a further 5 hours and then cooled to room temperature and diluted with AcOEt. The organic phase was filtered through celite and washed with water then brine, dried and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel [10-20% EtOAc/cyclohexane] gave the title compound (200 mg, 36%) as a colourless oil. MS (ES) C16H19N3O2 requires 285, found 286 [M+H]+.

Workup

  1. temperatureheated for a further 5 hours
  2. temperaturecooled to room temperature
  3. filtrationThe organic phase was filtered through celite
  4. washwashed with water
  5. dry with materialbrine, dried
  6. concentrationconcentrated in vacuo
  7. customPurification of the residue by flash chromatography on silica gel [10-20% EtOAc/cyclohexane]

Sources & evidence

ORD record
ord-27cb0a3f63ac452fa8a1a777b72b6245
Source dataset
uspto-grants-2012_12
Patent number
US08324254B2

Reaction notes

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