Triphenylarsine → HCID 21063260, compound

HRID 852248Notes

Reaction equation

HRID 852248 reaction equation
Br[C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[Li+].[Cl-].C1C=CC([As](C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[CH3:31][O:32][C:33](=[O:54])[C@@H:34]([NH:46][C:47]([O:49][C:50]([CH3:53])([CH3:52])[CH3:51])=[O:48])[CH2:35][C:36]1[CH:41]=[CH:40][C:39]([Sn](C)(C)C)=[CH:38][CH:37]=1>CN1CCCC1=O.CCOC(C)=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]>[CH3:31][O:32][C:33](=[O:54])[C@@H:34]([NH:46][C:47]([O:49][C:50]([CH3:52])([CH3:51])[CH3:53])=[O:48])[CH2:35][C:36]1[CH:41]=[CH:40][C:39]([C:2]2[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=2[C:4]#[N:5])=[CH:38][CH:37]=1

Participants

8

Reactant 4

HCID 11773TriphenylarsineHCID 162722-BromobenzonitrileHCID 433294Lithium ChlorideHCID 11144703HCID 11144703, compound

Product 1

HCID 21063260HCID 21063260, compoundYield 54%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent2×

Conditions

Temperature
80 °C

Procedure

In a dry 25 ml round bottom flask fitted with a reflux condenser vented through a three way valve attached to a vacuum source and nitrogen gas, 2-bromobenzonitrile (557 mg, 3.06 mmol), tris(dibenzylideneacetone)dipalladium (0), (51 mg, 0.056 mmol), LiCl (353 mg, 8.34 mmol), and AsPh3 (68 mg, 0.22 mmol) were added, followed by 13 ml of N-methylpyrrolidinone. The mixture was degassed and stirred for 10 minutes. A solution of (S)-2-tert-butoxycarbonylamino-3-(4-trimethylstannylphenyl) propionic acid methyl ester (1.23 g, 2.78 mmol) in N-methylpyrrolidinone (4.5 ml) was then added and the reaction was heated at 80° C. for 5 h and left overnight at room temperature. The reaction mixture was diluted with EtOAc (25 ml), quenched by addition of 10 ml of saturated KF solution and stirred for 20 minutes. The reaction mixture was partitioned between water (40 ml) and EtOAc (100 ml). The organic layer was separated, washed with water (6×40 mil and dried (MgSO4). The solvents were removed under reduced pressure and the resulting crude was purified by flash chromatography (9:1 to 7:3 hexanes/EtOAc) to give (S)-2-tert-butoxycarbonylamino-3-(2′-cyano-biphenyl-4-yl) propionic acid methyl ester (570 mg, 54%) as a white solid.

Workup

  1. customIn a dry 25 ml round bottom flask fitted with a reflux condenser
  2. additionwere added
  3. customThe mixture was degassed
  4. waitleft overnight at room temperature
  5. customquenched by addition of 10 ml of saturated KF solution
  6. stirringstirred for 20 minutes
  7. customThe reaction mixture was partitioned between water (40 ml) and EtOAc (100 ml)
  8. customThe organic layer was separated
  9. washwashed with water (6×40 mil
  10. dry with materialdried (MgSO4)
  11. customThe solvents were removed under reduced pressure
  12. customthe resulting crude was purified by flash chromatography (9:1 to 7:3 hexanes/EtOAc)

Sources & evidence

ORD record
ord-09affe1f23214f6984111eca535f291c
Source dataset
uspto-grants-2007_08
Patent number
US07253171B2

Reaction notes

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