Triphenylphosphine → HCID 69086079, compound

HRID 2362452Notes

Reaction equation

HRID 2362452 reaction equation
Br[C:2]1[CH:3]=[C:4]([C@@H:9]2[C@@H:13]([C:14]3[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=3)[O:12][C:11](=[O:21])[NH:10]2)[C:5]([F:8])=[N:6][CH:7]=1.[C:22]([C:24]1[CH:25]=[N:26][CH:27]=[CH:28][CH:29]=1)#[CH:23].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[F:8][C:5]1[C:4]([C@@H:9]2[C@@H:13]([C:14]3[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=3)[O:12][C:11](=[O:21])[NH:10]2)=[CH:3][C:2]([C:23]#[C:22][C:24]2[CH:25]=[N:26][CH:27]=[CH:28][CH:29]=2)=[CH:7][N:6]=1

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 1860033-EthynylpyridineHCID 69086172HCID 69086172, compound

Product 1

HCID 69086079HCID 69086079, compoundYield 71.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
90 °C

Procedure

To a 15 ml sealable vial was added a mixture of (4R,5R)-4-(5-bromo-2-fluoropyridin-3-yl)-5-(4-fluorophenyl)oxazolidin-2-one (270 mg, 0.760 mmol) in triethylamine (15 mL). To this suspension was added 3-ethynylpyridine (94 mg, 0.912 mmol), triphenylphosphine (59.8 mg, 0.228 mmol) and copper(I) iodide (2.90 mg, 0.015 mmol). The solution was degassed with nitrogen for 20 min, then bis(triphenylphosphine)palladium(II) chloride (10.67 mg, 0.015 mmol) was quickly added and the vial was sealed, heated to 90° C., and allowed to stir overnight. The next day the suspension had turned homogeneous and the reaction was cooled to room temperature and the solvent was evaporated in vacuo. The crude residue was purified by silica gel chromotagraphy 2% MeOH/98% CH2Cl2 affording (4R,5R)-4-(2-fluoro-5-(pyridin-3-ylethynyl)pyridin-3-yl)-5-(4-fluorophenyl)oxazolidin-2-one (210 mg, 0.540 mmol, 71.0% yield) 1H-NMR (CDCl3, 400 MHz) δ 8.82 (s, 1H), 8.64 (d, J=4.0, 1H), 8.44 (s, 1H), 8.14 (d, J=8.0, 1H), 7.86, (d, J=8.0, 1H), 7.44-7.40 (m, 2H), 7.38-7.36 (m, 1H), 7.19-7.15 (m, 2H), 5.64 (brs, 1H), 5.38 (d, J=4.0, 1H), 5.05 (d, J=4.0, 1H), LC/Mass spec. (Analytical HPLC method 2): RT=1.78 min. Mass=378.16 (MH)+.

Workup

  1. additionTo a 15 ml sealable vial was added
  2. customThe solution was degassed with nitrogen for 20 min
  3. customthe vial was sealed
  4. temperaturethe reaction was cooled to room temperature
  5. customthe solvent was evaporated in vacuo
  6. customThe crude residue was purified by silica gel chromotagraphy 2% MeOH/98% CH2Cl2

Sources & evidence

ORD record
ord-0e3ef8992b8b4195b9601659d8e71817
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

Loading…