Dimethylformamide → Tert-butyl 6-cyano-4-oxo-3,4-dihydrospiro[1-benzopyran-2,4'-piperidine]-1'-carboxylate

HRID 545199Notes

Reaction equation

HRID 545199 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:21](=[CH:22][CH:23]=1)[O:20][C:7]1([CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]1)[CH2:6][C:5]2=[O:24].[CH3:25][N:26](C=O)C>C(OCC)(=O)C.[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:25]([C:2]1[CH:3]=[C:4]2[C:21](=[CH:22][CH:23]=1)[O:20][C:7]1([CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:17])([CH3:19])[CH3:18])=[O:14])[CH2:9][CH2:8]1)[CH2:6][C:5]2=[O:24])#[N:26]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 2794759tert-Butyl 6-bromo-4-oxospiro[chroman-2,4'-piperidine]-1'-carboxylate

Product 1

HCID 66649586Tert-butyl 6-cyano-4-oxo-3,4-dihydrospiro[1-benzopyran-2,4'-piperidine]-1'-carboxylate

Reagents, catalysts & solvents 3

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

Conditions

Temperature
90 °C

Procedure

A mixture of tert-butyl 6-bromo-4-oxospiro[chroman-2,4′-piperidine]-1′-carboxylate (143 g, 0.36 mol), Zn(CN)2 (84.7 g, 0.72 mol), Pd(PPh3)4 (20 g, 17 mmol) and dry DMF (1 liter) was stirred under an argon atmosphere at 90° C. for 6 hours. The resulting mixture was, after cooled, diluted with ethyl acetate (1 liter), and washed with aqueous 12% ammonia, water, and saturated brine in order. The organic layer was dried over sodium sulfate, and concentrated, and the residue was treated with methanol, and the resulting insoluble solid was taken out through filtration, and dried under a reduced pressure to obtain tert-butyl 6-cyano-4-oxospiro[chroman-2,4′-piperidine]-1′-carboxylate as a colorless solid.

Workup

  1. temperatureafter cooled
  2. washwashed with aqueous 12% ammonia, water, and saturated brine in order
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. concentrationconcentrated
  5. additionthe residue was treated with methanol
  6. filtrationthe resulting insoluble solid was taken out through filtration
  7. customdried under a reduced pressure

Sources & evidence

ORD record
ord-b7a63fc35a524e949031d11038a80875
Source dataset
uspto-grants-2011_05
Patent number
US07935712B2

Reaction notes

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