Triphenylarsine → (5R)-(-)-3-[4-(3-pyridyl)-3-fluorophenyl]-2-oxo-5-oxazolidinecarboxamide

HRID 1826197Notes

Reaction equation

HRID 1826197 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N:9]2[CH2:13][C@H:12]([C:14]([NH2:16])=[O:15])[O:11][C:10]2=[O:17])[CH:5]=[CH:6][C:7]=1I.C[Sn](C)(C)[C:20]1[CH:21]=[N:22][CH:23]=[CH:24][CH:25]=1.C1([As](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN1CCCC1=O.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[Cu]I>[N:22]1[CH:23]=[CH:24][CH:25]=[C:20]([C:7]2[CH:6]=[CH:5][C:4]([N:9]3[CH2:13][C@H:12]([C:14]([NH2:16])=[O:15])[O:11][C:10]3=[O:17])=[CH:3][C:2]=2[F:1])[CH:21]=1

Participants

8

Reactant 3

HCID 11773Triphenylarsine2×HCID 108684453-(Trimethylstannyl)pyridineHCID 68487894(5R)-(-)-3-[3-fluoro-4-iodophenyl]-2-oxo-5-oxazolidinecarboxamide

Product 1

HCID 10214934(5R)-(-)-3-[4-(3-pyridyl)-3-fluorophenyl]-2-oxo-5-oxazolidinecarboxamide

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst2×HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 962WaterSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of (5R)-(−)-3-[3-fluoro-4-iodophenyl]-2-oxo-5-oxazolidinecarboxamide (Step 3, 422 mg, 1.21 mmol), 3-(trimethylstannyl)pyridine (Step 4, 350 mg, 1.45 mmol), tris(dibenzylideneacetone)dipalladium(0) (22 mg, 0.0242 mmol), triphenylarsine (59 mg, 0.194 mmol) and copper(I) iodide (9 mg, 0.0484 mmol) in N-methyl-2-pyrrolidinone (4.8 mL) under nitrogen was degassed, heated up to 50° C. and stirred at this temperature for 2 days, during which additional tris(dibenzylideneacetone)dipalladium(0) (22 mg, 0.0242 mmol), triphenylarsine (59 mg, 0.194 mmol) and copper(I) iodide (9 mg, 0.0484 mmol) are added. The resulting mixture was diluted with water (15 mL) and extracted with methylene chloride (3×20 mL), and the combined organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting oil was diluted with ethyl acetate (25 mL) and extracted with aqueous hydrochloric acid (1M, 25 mL), and the aqueous phase was neutralized with sodium hydroxide (s), saturated with sodium chloride and extracted with methylene chloride (3×25 mL) containing a small amount of methanol. This combined organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue was recrystallized from ethyl acetate/hexane to give the title compound, mp 240-242° C. (dec.); MS (ESI+) for C15H12FN3O3 m/z 302 (M+H)+; [α]25D=−25 (c 0.94, DMSO).

Workup

  1. customwas degassed
  2. additionare added
  3. extractionextracted with methylene chloride (3×20 mL)
  4. dry with materialthe combined organic phase was dried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. additionThe resulting oil was diluted with ethyl acetate (25 mL)
  7. extractionextracted with aqueous hydrochloric acid (1M, 25 mL)
  8. extractionextracted with methylene chloride (3×25 mL)
  9. additioncontaining a small amount of methanol
  10. dry with materialThis combined organic phase was dried over anhydrous sodium sulfate
  11. concentrationconcentrated under reduced pressure
  12. customthe residue was recrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-93ae7e3afe064a70ab6a4860f8cb8db3
Source dataset
uspto-grants-2006_05
Patent number
US07049443B2

Reaction notes

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