Dimethylformamide → Tert-butyl 9-cyano-2,3-dihydrobenzo[F][1,4]oxazepine-4(5H)-carboxylate

HRID 1514226Notes

Reaction equation

HRID 1514226 reaction equation
FC(F)(F)S(O[C:7]1[C:17]2[O:16][CH2:15][CH2:14][N:13]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:12][C:11]=2[CH:10]=[CH:9][CH:8]=1)(=O)=O.[CH3:27][N:28](C=O)C>CCOC(C)=O.O.[C-]#N.[Zn+2].[C-]#N.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:27]([C:7]1[C:17]2[O:16][CH2:15][CH2:14][N:13]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:12][C:11]=2[CH:10]=[CH:9][CH:8]=1)#[N:28]

Participants

7

Reactant 2

HCID 6228DimethylformamideHCID 594035221,1-Dimethylethyl 9-{[(trifluoromethyl)sulfonyl]oxy}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

Product 1

HCID 54757009Tert-butyl 9-cyano-2,3-dihydrobenzo[F][1,4]oxazepine-4(5H)-carboxylate

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 1,1-dimethylethyl 9-{[(trifluoromethyl)sulfonyl]oxy}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (Preparation 63) (9 g, 22.65 mmol), zinc cyanide (3.99 g, 34.0 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.62 g, 2.265 mmol) in DMF (90 ml) was heated at 80° C. for 24 hrs. The reaction was cooled, diluted with EtOAc (400 ml) and water (400 ml) and filtered to remove insoluble material. The filtrate was separated and the organic layer washed with water, dried over magnesium sulphate and evaporated. Purified by flash chromatography eluting with EtOAc/iso-hexane 1:9 then 1:3 to give the title compound (5.1 g) as a colourless oil. MS (ES): C15H18N2O3 requires 274; found 174 [M+H−100]+.

Workup

  1. temperatureThe reaction was cooled
  2. filtrationfiltered
  3. customto remove insoluble material
  4. customThe filtrate was separated
  5. washthe organic layer washed with water
  6. dry with materialdried over magnesium sulphate
  7. customevaporated
  8. customPurified by flash chromatography
  9. washeluting with EtOAc/iso-hexane 1:9

Sources & evidence

ORD record
ord-f32031c2f2da41bf85ab343fa26c23b5
Source dataset
uspto-grants-2012_07
Patent number
US08222245B2

Reaction notes

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