Reaction equation
CC(OC([N:8]1[CH2:14][CH2:13][C:12](=[O:15])[CH:11](Br)[CH2:10][CH2:9]1)=O)(C)C.CC(OC(N1CCCC(=O)C(Br)C1)=O)(C)C.[C:33]([NH2:43])(=O)/[CH:34]=[CH:35]/[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1>>[C:36]1(/[CH:35]=[CH:34]/[C:33]2[O:15][C:12]3[CH2:13][CH2:14][NH:8][CH2:9][CH2:10][C:11]=3[N:43]=2)[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1Participants
Conditions
- Temperature
- 120 °C
Procedure
A mixture of 4-bromohexahydro-5-oxo-1H-azepine-1-carboxylic acid 1,1-dimethylethyl ester and 3-bromohexahydro-4-oxo-1H-azepine-1-carboxylic acid 1,1-dimethylethyl ester (0.22 g, 0.50 mmol) and trans-cinnamamide (0.06 g, 0.38 mmol) was supported in silica gel (1 g) and mechanically stirred at 120° C. for 3 days. The product was eluted from the silica gel with a 7M solution of ammonia in MeOH and the filtrate evaporated in vacuo. The crude product was basified with a saturated solution of NaHCO3 and extracted with DCM. The organic layer was separated, dried (Na2SO4), filtered and the solvent evaporated in vacuo to yield 5,6,7,8-tetrahydro-2-[(E)-2-phenylethenyl]-4H-oxazolo[4,5-d]azepine (0.045 g, 15% yield, 32% pure) as a brown solid that was used in the next step without further purification. C15H16N2O LCMS: Rt 1.60, m/z 241 [M+H]+ (method 5). The compound 3-bromohexahydro-4-oxo-1H-azepine-1-carboxylic acid 1,1-dimethylethyl ester was not observed in the crude of the reaction.
Workup
- washThe product was eluted from the silica gel with a 7M solution of ammonia in MeOH
- customthe filtrate evaporated in vacuo
- extractionextracted with DCM
- customThe organic layer was separated
- dry with materialdried (Na2SO4)
- filtrationfiltered
- customthe solvent evaporated in vacuo
Sources & evidence
- ORD record
- ord-feb9b4fcb67a4ad9888ea1dadc344e06
- Source dataset
- uspto-grants-2015_07
- Patent number
- US09090632B2
Linked notes
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