Cesium carbonate → HCID 131736368, compound

HRID 1055470Notes

Reaction equation

HRID 1055470 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].[CH3:7][N:8]([C@@H:16]([CH3:37])[C:17](=[O:36])[NH:18][C@H:19]1[C:25]2([CH2:30][CH2:29][O:28][CH2:27][CH2:26]2)[O:24][C:23]2[CH:31]=[CH:32][CH:33]=[CH:34][C:22]=2[NH:21][C:20]1=[O:35])[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12].C1C(=O)N([Br:45])C(=O)C1>CN(C=O)C.[NH4+].[Cl-]>[Br:45][C:32]1[CH:33]=[CH:34][C:22]2[NH:21][C:20](=[O:35])[C@@H:19]([NH:18][C:17](=[O:36])[C@@H:16]([N:8]([CH3:7])[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:12])[CH3:13])[CH3:37])[C:25]3([CH2:26][CH2:27][O:28][CH2:29][CH2:30]3)[O:24][C:23]=2[CH:31]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 67184N-bromobutanimideHCID 90037528HCID 90037528, compound

Product 1

HCID 131736368HCID 131736368, compoundYield 127%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
0 °C

Procedure

Cs2CO3 (331 mg, 1.01 mmol, Eq: 2.2) was added was added to a solution of tert-butyl methyl((S)-1-oxo-1-((S)-4-oxo-2′,3′,4,5,5′,6′-hexahydro-3H-spiro[benzo[b][1,4]oxazepine-2,4′-pyran]-3-ylamino)propan-2-yl)carbamate (200 mg, 461 μmol, Eq: 1.00) and DMF (10 mL) and the mixture was cooled to 0° C. and a solution of NBS (82.1 mg, 461 μmol, Eq: 1.00) in 2 mL DMF was added dropwise over 5 min. and the mixture warmed to RT. After 10 h the mixture was diluted with sat. NH4Cl and extracted with EtOAc. The combined extracts were washed with H2O, concentrated and the residue was purified by preparative TLC to give tert-butyl (S)-1-((S)-8-bromo-4-oxo-2′,3′,4,5,5′,6′-hexahydro-3H-spiro[benzo[b][1,4]oxazepine-2,4′-pyran]-3-ylamino)-1-oxopropan-2-yl(methyl)carbamate (300 mg, 98%).

Workup

  1. temperaturethe mixture warmed to RT
  2. extractionextracted with EtOAc
  3. washThe combined extracts were washed with H2O
  4. concentrationconcentrated
  5. customthe residue was purified by preparative TLC

Sources & evidence

ORD record
ord-bd084e355ad3453bb44746f572005c47
Source dataset
uspto-grants-2016_07
Patent number
US09394263B2

Reaction notes

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