Ethyl Acetate → (S)-tert-butyl (1-(4-amino-6-bromo-5-(quinolin-3-yl)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)but-3-en-2-yl)carbamate

HRID 336162Notes

Reaction equation

HRID 336162 reaction equation
[Br:1]N1C(=O)CCC1=O.[NH2:9][C:10]1[C:11]2[C:18]([C:19]3[CH:20]=[N:21][C:22]4[C:27]([CH:28]=3)=[CH:26][CH:25]=[CH:24][CH:23]=4)=[CH:17][N:16]([CH2:29][C@@H:30]([NH:33][C:34](=[O:40])[O:35][C:36]([CH3:39])([CH3:38])[CH3:37])[CH:31]=[CH2:32])[C:12]=2[N:13]=[CH:14][N:15]=1.S([O-])([O-])(=O)=S.[Na+].[Na+].C(OCC)(=O)C>CN(C=O)C>[NH2:9][C:10]1[C:11]2[C:18]([C:19]3[CH:20]=[N:21][C:22]4[C:27]([CH:28]=3)=[CH:26][CH:25]=[CH:24][CH:23]=4)=[C:17]([Br:1])[N:16]([CH2:29][C@@H:30]([NH:33][C:34](=[O:40])[O:35][C:36]([CH3:39])([CH3:38])[CH3:37])[CH:31]=[CH2:32])[C:12]=2[N:13]=[CH:14][N:15]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 24477Sodium ThiosulfateHCID 67184N-bromobutanimideHCID 86711294HCID 86711294, compound

Product 1

HCID 86711295(S)-tert-butyl (1-(4-amino-6-bromo-5-(quinolin-3-yl)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)but-3-en-2-yl)carbamateYield 66.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
-15 °C

Procedure

N-Bromosuccinimide (3.63 g) was added to a solution of (S)-tert-butyl (1-(4-amino-5-(quinolin-3-yl)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)but-3-en-2-yl)carbamate (7.98 g) obtained in Step 3 in DMF (64 ml) at −15° C., and the mixture was stirred at −15° C. for 1 hour. A 10% aqueous sodium thiosulfate solution and ethyl acetate were added to the reaction mixture, and stirred at room temperature for 10 minutes. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate twice. The resulting organic layer was washed with a saturated sodium chloride solution twice, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate/methanol) to obtain the title compound (6.30 g) as a light-brown solid.

Workup

  1. stirringstirred at room temperature for 10 minutes
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted with ethyl acetate twice
  4. washThe resulting organic layer was washed with a saturated sodium chloride solution twice
  5. dry with materialdried over anhydrous magnesium sulfate
  6. distillationThe solvent was distilled off under reduced pressure
  7. customThe resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate/methanol)

Sources & evidence

ORD record
ord-12c25ebdeea34a2695b640d1e795f681
Source dataset
uspto-grants-2014_11
Patent number
US08889666B2

Reaction notes

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