Dimedone → HCID 90022794, compound

HRID 626436Notes

Reaction equation

HRID 626436 reaction equation
C(OC([NH:7][C@H:8]([C:15]([NH:17][C:18]1[CH:19]=[C:20]([CH2:25][C@H:26]([CH3:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH:21]=[CH:22][C:23]=1[Cl:24])=[O:16])[CH:9]([C:11]([F:14])([F:13])[F:12])[CH3:10])=O)C=C.CC1(C)CC(=O)CC(=O)C1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1COCC1>[Cl:24][C:23]1[CH:22]=[CH:21][C:20]([CH2:25][C@H:26]([CH3:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28])=[CH:19][C:18]=1[NH:17][C:15](=[O:16])[C@H:8]([CH:9]([C:11]([F:14])([F:13])[F:12])[CH3:10])[NH2:7]

Participants

5

Reactant 2

HCID 31358DimedoneHCID 126504149HCID 126504149, compound

Product 1

HCID 90022794HCID 90022794, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

2.24 g (4.68 mmol) of ethyl (2S)-3-[3-({N-[(allyloxy)carbonyl]-4,4,4-trifluorovalyl}amino)-4-chlorophenyl]-2-methylpropanoate (Example 39A, mixture of 4 isomers) and 5.25 g (37.4 mmol) of dimedone were initially charged in 25 ml of abs. THF. At RT, the solution was deoxygenated by passing through argon for 30 min Subsequently 108.1 mg (0.094 mmol) of tetrakis(triphenylphosphine)palladium(0) were added and the mixture was stirred at RT overnight. After dilution with ethyl acetate, the mixture was washed twice with sat. sodium bicarbonate solution and once with sat. sodium chloride solution. The organic phase was dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 40:1→20:1) and separated. This gave 1.65 g of the target compound as diastereomer mixture 1 (89.4% of theory).

Workup

  1. customAt RT, the solution was deoxygenated
  2. washAfter dilution with ethyl acetate, the mixture was washed twice with sat. sodium bicarbonate solution and once with sat. sodium chloride solution
  3. dry with materialThe organic phase was dried over magnesium sulphate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 40:1→20:1)
  6. customseparated

Sources & evidence

ORD record
ord-27266fae19dc4182b4efeb5a475ec0d1
Source dataset
uspto-grants-2016_04
Patent number
US09309198B2

Reaction notes

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