Triphenylphosphine → Tert-butyl[(5-chloro-3-{[3-(propylsulfonyl)phenyl]ethynyl}pyridin-2-yl)oxy]acetate

HRID 2390241Notes

Reaction equation

HRID 2390241 reaction equation
[C:1]([O:5][C:6](=[O:17])[CH2:7][O:8][C:9]1[C:14](Br)=[CH:13][C:12]([Cl:16])=[CH:11][N:10]=1)([CH3:4])([CH3:3])[CH3:2].[C:18]([C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([S:26]([CH2:29][CH2:30][CH3:31])(=[O:28])=[O:27])[CH:21]=1)#[CH:19].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[C:1]([O:5][C:6](=[O:17])[CH2:7][O:8][C:9]1[C:14]([C:19]#[C:18][C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([S:26]([CH2:29][CH2:30][CH3:31])(=[O:28])=[O:27])[CH:21]=2)=[CH:13][C:12]([Cl:16])=[CH:11][N:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 565942671-Ethynyl-3-(propylsulfonyl)benzene2×HCID 58521889Tert-butyl[(3-bromo-5-chloropyridin-2-yl)oxy]acetate2×

Product 1

HCID 58521947Tert-butyl[(5-chloro-3-{[3-(propylsulfonyl)phenyl]ethynyl}pyridin-2-yl)oxy]acetate

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of tert-butyl[(3-bromo-5-chloropyridin-2-yl)oxy]acetate (Intermediate 182; 160 mg; 0.50 mmol), 1-ethynyl-3-(propane-1-sulfonyl)-benzene (Intermediate 42; 155 mg; 0.74 mmol), bis(triphenylphosphine)palladium (II) chloride (10 mg; 0.01 mmol) and triphenylphosphine (26 mg; 0.10 mmol) is treated with cuprous iodide (3 mg; 0.01 mmol) and TEA (1.10 ml) and heated at 90° C. in a sealed vessel for 15 hours. The mixture was diluted with EtOAc and washed with a saturated NH4Cl solution and brine. The organic phase was dried over MgSO4, concentrated to dryness under reduced pressure affording a sticky solid, which was purified by column chromatography (silica), eluting with cyclohexane containing increasing amounts of EtOAc, affording the title compound as a yellow sticky solid

Workup

  1. washwashed with a saturated NH4Cl solution and brine
  2. dry with materialThe organic phase was dried over MgSO4
  3. concentrationconcentrated to dryness under reduced pressure
  4. customaffording a sticky solid, which
  5. customwas purified by column chromatography (silica)
  6. washeluting with cyclohexane containing
  7. temperatureincreasing amounts of EtOAc

Sources & evidence

ORD record
ord-1b8c73d4737e48a9b00289a9c79a6708
Source dataset
uspto-grants-2012_09
Patent number
US08273769B2

Reaction notes

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