Tributylvinyltin → HCID 67457050, compound

HRID 1804515Notes

Reaction equation

HRID 1804515 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]=[C:11]([C:13]3[O:17][N:16]=[C:15]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=4)[C:14]=3[C:24]([F:27])([F:26])[F:25])[O:10][N:9]=2)=[CH:4][C:3]=1[CH3:28].[CH2:29]([Sn](CCCC)(CCCC)C=C)[CH2:30]CC.[Cl-].[Li+]>O1CCOCC1.C(OCC)(=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:28][C:3]1[CH:4]=[C:5]([C:8]2[N:12]=[C:11]([C:13]3[O:17][N:16]=[C:15]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=4)[C:14]=3[C:24]([F:27])([F:26])[F:25])[O:10][N:9]=2)[CH:6]=[CH:7][C:2]=1[CH:29]=[CH2:30]

Participants

7

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 67454058HCID 67454058, compound

Product 1

HCID 67457050HCID 67457050, compoundYield 44.4%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 3-(4-iodo-3-methylphenyl)-5-(3-phenyl-4-(trifluoromethyl)isoxazol-5-yl)-1,2,4-oxadiazole (1.45 g, 2.92 mmol) in dioxane (5 mL) in a sealed tube was added sequentially tributyl(vinyl)stannane (0.942 mL, 3.21 mmol) and lithium chloride (0.371 g, 8.75 mmol). The mixture was degassed under reduced pressure and charged with nitrogen (2×). To the mixture was added tetrakis(triphenylphosphine) palladium(0) (0.337 g, 0.292 mmol), and the mixture was stirred under a strong stream of nitrogen for 5 min. The reaction mixture was sealed, immersed in an oil bath at 100° C., and stirred overnight. The reaction mixture was diluted with ethyl acetate and filtered. The solid was rinsed with ethyl acetate (3×). The filtrate was concentrated, diluted with ether, and filtered under reduced pressure. HPLC indicated that the product was in the filtrate, which was concentrated under reduced pressure and purified by flash silica gel chromatography using a mixture of ethyl acetate in hexane (1%-2.5%) to give 3-(3-methyl-4-vinylphenyl)-5-(3-phenyl-4-(trifluoromethyl)isoxazol-5-yl)-1,2,4-oxadiazole (0.514 g, 1.294 mmol, 44.4% yield) as an white solid. The compound had an HPLC ret. time=3.85 min.−Column. CHROMOLITH® SpeedROD 4.6×50 mm (4 min.); Solvent A=10% MeOH, 90% H2O, 0.1% TFA; Solvent B=90% MeOH, 10% H2O, 0.1% TFA. MS M+1=398.0. 1H NMR (500 MHz, CDCl3) δ ppm 2.47 (s, 3H), 5.43-5.46 (m, 1H), 7.00 (dd, J=17.34, 10.96 Hz, 1H), 7.53-7.62 (m, 3H) 7.65 (d, J=8.32 Hz, 1H), 7.69 (d, J=6.94 Hz, 2H), and 7.99-8.04 (m, 2H).

Workup

  1. customThe mixture was degassed under reduced pressure
  2. additioncharged with nitrogen (2×)
  3. customThe reaction mixture was sealed
  4. customimmersed in an oil bath at 100° C.
  5. stirringstirred overnight
  6. filtrationfiltered
  7. washThe solid was rinsed with ethyl acetate (3×)
  8. concentrationThe filtrate was concentrated
  9. additiondiluted with ether
  10. filtrationfiltered under reduced pressure
  11. concentrationwas concentrated under reduced pressure
  12. custompurified by flash silica gel chromatography
  13. additiona mixture of ethyl acetate in hexane (1%-2.5%)

Sources & evidence

ORD record
ord-743c58e12a8f4fa783bb926a0ba24fde
Source dataset
uspto-grants-2013_01
Patent number
US08354398B2

Reaction notes

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