Water → (S)-3-((S)-1-(4-bromophenyl)ethyl)-6-(2-oxopropyl)-6-phenyl-1,3-oxazinan-2-one

HRID 1191790Notes

Reaction equation

HRID 1191790 reaction equation
[CH2:1]([C@@:4]1([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[O:9][C:8](=[O:10])[N:7]([C@H:11]([C:13]2[CH:18]=[CH:17][C:16]([Br:19])=[CH:15][CH:14]=2)[CH3:12])[CH2:6][CH2:5]1)[CH:2]=[CH2:3].[OH2:26]>CN(C=O)C.Cl[Cu].Cl[Pd]Cl>[Br:19][C:16]1[CH:15]=[CH:14][C:13]([C@@H:11]([N:7]2[CH2:6][CH2:5][C@:4]([CH2:1][C:2](=[O:26])[CH3:3])([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[O:9][C:8]2=[O:10])[CH3:12])=[CH:18][CH:17]=1

Participants

6

Reactant 2

HCID 962WaterHCID 59532360(R)-6-allyl-3-((S)-1-(4-bromophenyl)ethyl)-6-phenyl-1,3-oxazinan-2-one

Product 1

HCID 59532378(S)-3-((S)-1-(4-bromophenyl)ethyl)-6-(2-oxopropyl)-6-phenyl-1,3-oxazinan-2-oneYield 58%

Reagents, catalysts & solvents 3

HCID 24290Palladium ChlorideCatalystHCID 62652Cuprous chlorideCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of (R)-6-allyl-3-((S)-1-(4-bromophenyl)ethyl)-6-phenyl-1,3-oxazinan-2-one (20 g, 50 mmol) and CuCl (12.4 g, 125 mmol) in dry DMF (50 mL) was added H2O (12 mL) and PdCl2 (2.66 g, 15 mmol) at 0˜−5° C. After addition, the mixture was allowed to warm to rt gradually for 48 h under O2. After TLC showing the stating material had disappeared, the solid was filtered off. Water (200 mL) and EtOAc (50 mL) were added. The layers were separated and the aqueous layer was extracted with EtOAc (3×40 mL). The combined organic layer was washed with brine, dried over Na2SO4, filtered and concentrated to give a residue, which was purified by column chromatography to give (S)-3-((S)-1-(4-bromo-phenyl)ethyl)-6-(2-oxopropyl)-6-phenyl-1,3-oxazinan-2-one (12 g, 58%).

Workup

  1. additionAfter addition
  2. filtrationthe solid was filtered off
  3. additionWater (200 mL) and EtOAc (50 mL) were added
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc (3×40 mL)
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give a residue, which
  11. customwas purified by column chromatography

Sources & evidence

ORD record
ord-648487988c7a4928bfda2c9ba5d5649a
Source dataset
uspto-grants-2014_03
Patent number
US08680093B2

Reaction notes

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