Acetic Acid → (S)-tert-Butyl 3-(3-formylphenyl)-1-((4-methoxyphenyl)(methyl)amino)-1-oxopropan-2-ylcarbamate

HRID 1471635Notes

Reaction equation

HRID 1471635 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH2:9][C@H:10]([NH:23][C:24](=[O:30])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27])[C:11]([N:13]([C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=2)[CH3:14])=[O:12])[CH:6]=[CH:7][CH:8]=1)#N.C(O)(=[O:33])C>N1C=CC=CC=1.[Ni].O>[CH:1]([C:3]1[CH:4]=[C:5]([CH2:9][C@H:10]([NH:23][C:24](=[O:30])[O:25][C:26]([CH3:28])([CH3:27])[CH3:29])[C:11]([N:13]([C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=2)[CH3:14])=[O:12])[CH:6]=[CH:7][CH:8]=1)=[O:33]

Participants

6

Reactant 2

HCID 176Acetic AcidHCID 90289954(S)-tert-Butyl 3-(3-cyanophenyl)-1-((4-methoxyphenyl)(methyl)amino)-1-oxopropan-2-ylcarbamate

Product 1

HCID 90289977(S)-tert-Butyl 3-(3-formylphenyl)-1-((4-methoxyphenyl)(methyl)amino)-1-oxopropan-2-ylcarbamate

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 962WaterSolventHCID 1049PyridineSolvent

Conditions

Temperature
46 °C

Procedure

(S)-tert-Butyl 3-(3-cyanophenyl)-1-((4-methoxyphenyl)(methyl)amino)-1-oxopropan-2-ylcarbamate (2.7 g, 6.60 mmole) was dissolved in pyridine (18.6 ml) and acetic acid (9.3 ml). Raney Nickel (2.7 g of a slurry in H2O) was added and the resulting suspension was stirred at 46° C. overnight. The reaction was confirmed complete by reverse phase HPLC/MS. The reaction was cooled to room temperature and then filtered through celite. The filtrate was concentrated under reduced pressure and then partitioned between EtOAc and H2O. The aqueous layer was extracted with EtOAc (3×). The combined organics were washed with H2O (2×) and brine (2×). The organic layer was dried over MgSO4, filtered and concentrated. The crude produce was dried under high vacuum overnight and used without further purification. Yield was 2.70 g. MS (m/z) 413 [M+H]+.

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. filtrationfiltered through celite
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. custompartitioned between EtOAc and H2O
  5. extractionThe aqueous layer was extracted with EtOAc (3×)
  6. washThe combined organics were washed with H2O (2×) and brine (2×)
  7. dry with materialThe organic layer was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude produce
  11. customwas dried under high vacuum overnight
  12. customused without further purification

Sources & evidence

ORD record
ord-3f957aff861d47c59aed697c6cfed68a
Source dataset
uspto-grants-2015_04
Patent number
US09012441B2

Reaction notes

Loading…