Triphenylarsine → HCID 86748479, compound

HRID 275190Notes

Reaction equation

HRID 275190 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][CH:14]=[CH:13][C:8]=1[C:9]([O:11][CH3:12])=[O:10])(=O)=O.C1([As](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:38][C:39]1([CH3:72])[CH2:48][CH2:47][C:46]([CH3:50])([CH3:49])[C:45]2[CH:44]=[C:43]([CH2:51][O:52][C:53]3[CH:58]=[CH:57][CH:56]=[CH:55][C:54]=3[Sn](CCCC)(CCCC)CCCC)[CH:42]=[CH:41][C:40]1=2.[Cl-].[Li+].[F-].[K+]>CN1CCCC1=O.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].[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.CCOCC>[CH3:38][C:39]1([CH3:72])[CH2:48][CH2:47][C:46]([CH3:49])([CH3:50])[C:45]2[CH:44]=[C:43]([CH2:51][O:52][C:53]3[CH:54]=[CH:55][CH:56]=[CH:57][C:58]=3[C:7]3[C:8]([C:9]([O:11][CH3:12])=[O:10])=[CH:13][CH:14]=[CH:15][CH:16]=3)[CH:42]=[CH:41][C:40]1=2

Participants

12

Reactant 5

HCID 11773Triphenylarsine3×HCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 11011497methyl 2-trifluoromethanesulfonyloxybenzoateHCID 20090605HCID 20090605, compound

Product 1

HCID 86748479HCID 86748479, compoundYield 40%

Reagents, catalysts & solvents 6

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst3×HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent2×

Conditions

Temperature
67 °C

Procedure

2-(Trifluoromethylsulphonyloxy)-benzoic acid, methyl ester (54) (0.486 g., 1.71 mmol, 1 equiv.) is dissolved in 3 mL of N-methylpyrrolidone and the solution is degassed. Tris(dibenzylideneacetone)dipalladium (0.156 g., 0.17 mmol, 0.10 equiv.) and triphenylarsine (0.080 g., 0.26 mmol, 0.15 equiv.) are added, followed by a solution of 2-[5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl]methoxyphenyl-tributylstannane (53) (1.00 g., 1.71 mmol, 1 equiv.) in 4 mL of N-methylpyrrolidone. The solution is heated to 67° C. for 5.5 hours with little conversion to product. More tris(dibenzylideneacetone)dipalladium (0.020 mg, 0.022 mmol, 0.01 equiv.) is added and heating continued 22 hours. More tris(dibenzylideneacetone)dipalladium 0.100 g., 0.11 mmol, 0.06 equiv.) and triphenylarsine (0.070 g., 0.23 mmol, 0.13 equiv.) are added along with lithium chloride (0.217 g., 5.10 mmol, 3 equiv.), and heating is continued. After 29 hours, more tris (dibenzylideneacetone) dipalladium (0. 060 g., 0.07 mmol, 0.04 equiv.) and triphenylarsine (0.030 g., 0.10 mmol, 0.06 equiv.) are added, and heating continued for 46 hours. The mixture is allowed to cool to room temperature, and 2 mL of ether is added, followed by 3 mL of saturated aqueous KF solution. After stirring for 30 minutes, the mixture is diluted with water and EtOAc and then filtered. The brown solids are washed with EtOAc, and the filtrate placed in a separatory funnel. The phases are separated, and the aqueous phase is extracted twice with EtOAc. The combined organic phase is washed with 3% aqueous ammonia, and then brine. The extracts are dried (MgSO4) and concentrated. The crude material is chromatographed on silica gel using EtOAc/hexane to afford 2-[5,6,7,8-tetrahydro-5,5,8,8-tetramethyl- 2-naphthalenyl]methoxy-[1,1'-biphenyl]-2'-carboxylic acid, methyl ester (55) (0.290 g., 0.68 mmol, 40%) as an oil: 1H NMR (300 MHz, CDCl3) δ 7.93 (dd, J=2, 8 Hz, 1H, ArH), 7.51 (ddd, J=2, 8, 8 Hz, 1H, ArH), 7.39-7.31 (m, 3H, ArH), 7.24-7.20 (m, 2H, ArH), 7.11 (d, J=2 Hz, 1H, ArH), 7.04 (m, 2H, ArH), 6.98 (dd, J=2, 8 Hz, 1H, ArH), 4.93 (s, 2H, ArCH2O), 3.55 (s, 3H, CO2CH3), 1.63 (s, 4H, CH2CH2), 1.23 (s, 6H, 2×CH3), 1.17 (s, 6H, 2×CH3); 13C NMR (75 MHz, CDCl3) δ 168.15 (C=0), 155.52, 144.81, 144.02, 139.54, 134.01, 131.54, 131.47, 131.20, 129.94, 129.71, 128.70, 127.02, 126.34, 124.79, 123.89, 120.92, 112.28, 70.25, 51.62, 35.14, 35.05, 34.24, 34.07, 31.84, 31.67; IR (film) 2958, 2926, 1732, 1598, 1500, 1482, 1456, 1446, 1290, 1252, 1222, 1120, 1086, 740 cm-1 ; MS (DCI) m/e 429 (MH+), 397 (M-CH3O), 201 (C15H21+).

Workup

  1. customthe solution is degassed
  2. temperatureheating
  3. temperatureheating
  4. waitAfter 29 hours
  5. temperatureheating
  6. waitcontinued for 46 hours
  7. temperatureto cool to room temperature
  8. filtrationfiltered
  9. washThe brown solids are washed with EtOAc
  10. customthe filtrate placed in a separatory funnel
  11. customThe phases are separated
  12. extractionthe aqueous phase is extracted twice with EtOAc
  13. washThe combined organic phase is washed with 3% aqueous ammonia
  14. dry with materialThe extracts are dried (MgSO4)
  15. concentrationconcentrated
  16. customThe crude material is chromatographed on silica gel

Sources & evidence

ORD record
ord-a0d7c5d725fe4513875bd6625b571e70
Source dataset
uspto-grants-1995_02
Patent number
US05391817

Reaction notes

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