Lithium Chloride → 3-(2-Pyridyl)-phenyl acetic acid methyl ester

HRID 1058572Notes

Reaction equation

HRID 1058572 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH2:8][C:9]([O:11][CH3:12])=[O:10])[CH:5]=[CH:6][CH:7]=1.FC(F)(F)S(O[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=1)(=O)=O.[Cl-].[Li+].C[Sn](C)C.C[Sn](C)C.[F-].[K+].CCOC(C)=O>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O1CCOCC1>[CH3:12][O:11][C:9](=[O:10])[CH2:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=2)[CH:3]=1

Participants

8

Reactant 5

HCID 433294Lithium ChlorideHCID 39476262-Pyridyl TrifluoromethanesulfonateHCID 6327618HexamethylditinHCID 11746402Methyl 2-(3-bromophenyl)acetateHCID 131723761HCID 131723761, compound

Product 1

HCID 543647723-(2-Pyridyl)-phenyl acetic acid methyl esterYield 48%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

Methyl 3-bromophenylacetate (25 g, 0.109 mol), 2-(trifluoro-methylsulfonyloxy)-pyridine (24.8 g, 0.109 mol), anhydrous lithium chloride (13.89 g, 0.3275 mol), and tetrakis(triphenylphosphine)palladium (6.31 g, 0.0055 mol) were combined, followed by hexamethylditin (35.8 g, 0.109 mol) and anhydrous dioxane (300 ml). The mixture was stirred at reflux for 16h, cooled, and poured into 1:1 saturated KF-EtOAc (1.6 L). The mixture was stirred at RT for 2 h, filtered, and the filtrate was washed with saturated aqueous NaHCO3 (200 ml) and with brine (200 ml), dried (MgSO4), and concentrated in vacuo to give a brown oil. The residue was flash chromatographed (silica gel, 1:4 EtOAc:hexane) to give the title compound as a yellow oil (11.9 g. 48% yield): MS(ES+) 228.1 (MH+). cf. Tetrahedron Letters, 1995, 36, 9085-9088

Workup

  1. temperaturecooled
  2. stirringThe mixture was stirred at RT for 2 h
  3. filtrationfiltered
  4. washthe filtrate was washed with saturated aqueous NaHCO3 (200 ml) and with brine (200 ml)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customto give a brown oil
  8. customchromatographed (silica gel, 1:4 EtOAc:hexane)

Sources & evidence

ORD record
ord-9432548c5cd54f3486a150f974b20d41
Source dataset
uspto-grants-2003_02
Patent number
US06518267B1

Reaction notes

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