tert-Butylsulfinamide, (R)-(+)- → HCID 86707914, compound

HRID 932281Notes

Reaction equation

HRID 932281 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]([CH2:18][CH:19]=[CH2:20])[C:9]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)=O)[CH:5]=[CH:6][CH:7]=1.[CH3:21][C:22]([S@:25]([NH2:27])=[O:26])([CH3:24])[CH3:23]>C1COCC1.[Cl-].[Na+].O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Cl:1][C:2]1[CH:3]=[C:4]([C@@H:8]([CH2:18][CH:19]=[CH2:20])[C:9](=[N:27][S@@:25]([C:22]([CH3:24])([CH3:23])[CH3:21])=[O:26])[C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 67998715HCID 67998715, compound

Product 1

HCID 86707914HCID 86707914, compound

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

2-(3-Chlorophenyl)-1-(4-chlorophenyl)pent-4-en-1-one (Example 418, Step A, 48 g, 157 mmol), titanium(IV) ethoxide, technical grade (65.9 mL, 315 mmol) and (R)-(+)-2-methyl-2-propanesulfinamide (Combi-Blocks, San Diego, Calif., 33.1 g, 267 mmol) were dissolved in 400 mL of THF. The mixture was heated with stirring under reflux for eighteen hours. The reaction was cooled and poured into brine. The resulting white solid was removed by filtration, rinsing with ethyl acetate. Ethyl acetate was added to the biphasic filtrate and the layers separated. The organic layer was washed with brine, then dried with anhydrous magnesium sulfate and concentrated. The crude product was purified by three chromatographies (330 g RediSep® pre-packed silica gel column (Teledyne Isco, Lincoln, Nebr.), eluting with hexane:ethyl acetate, 95:5 to 85:5) to afford the title compound eluting second on silica gel TLC in hexane/ethyl acetate, the diastereomer (R)—N-((S)-2-(3-chlorophenyl)-1-(4-chlorophenyl)pent-4-en-1-ylidene)-2-methylpropane-2-sulfinamide eluting third on silica gel TLC in hexane/ethyl acetate, and some starting ketone eluting first on silica gel TLC in hexane/ethyl acetate.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for eighteen hours
  3. temperatureThe reaction was cooled
  4. customThe resulting white solid was removed by filtration
  5. washrinsing with ethyl acetate
  6. additionEthyl acetate was added to the biphasic filtrate
  7. customthe layers separated
  8. washThe organic layer was washed with brine
  9. dry with materialdried with anhydrous magnesium sulfate
  10. concentrationconcentrated
  11. customThe crude product was purified by three chromatographies (330 g RediSep® pre-packed silica gel column (Teledyne Isco, Lincoln, Nebr.), eluting with hexane:ethyl acetate, 95:5 to 85:5)

Sources & evidence

ORD record
ord-abef9fe7647c41faa7073b083da039e6
Source dataset
uspto-grants-2016_03
Patent number
US09296736B2

Reaction notes

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