Sodium Iodide → 5-(4-Fluorophenyl)-6-(4-methylsulfonylphenyl)spiro[2.4]hept-5-ene

HRID 2292983Notes

Reaction equation

HRID 2292983 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:12][C:11]([CH2:24]S(C3C=CC(C)=CC=3)(=O)=O)([CH2:13]S(C3C=CC(C)=CC=3)(=O)=O)[CH2:10][C:9]=2[C:35]2[CH:40]=[CH:39][C:38]([S:41]([CH3:44])(=[O:43])=[O:42])=[CH:37][CH:36]=2)=[CH:4][CH:3]=1.[I-].[Na+]>CN(C=O)C.[Zn]>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH2:12][C:11]3([CH2:10][C:9]=2[C:35]2[CH:36]=[CH:37][C:38]([S:41]([CH3:44])(=[O:42])=[O:43])=[CH:39][CH:40]=2)[CH2:24][CH2:13]3)=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 5238Sodium IodideHCID 189337191-[2-(4-Fluorophenyl)-4,4-di(tosylmethyl)cyclopenten-1-yl]-4-(methylsulfonyl)benzene

Product 1

HCID 98517705-(4-Fluorophenyl)-6-(4-methylsulfonylphenyl)spiro[2.4]hept-5-eneYield 86%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
150 °C

Procedure

Under nitrogen, a solution of 1.02 g (1.49 mmol) of 1-[2-(4-fluorophenyl)-4,4-di(tosylmethyl)cyclopenten-1-yl]-4-(methylsulfonyl)benzene (prepared in Step 10) in 24 mL of DMF was treated with 3.23 g (21.55 mmol) of sodium iodide and 1.61 g (24.63 mmol) of zinc dust. The reaction was stirred at 150° C. for 1.5 hour, concentrated in vacuo, and partitioned between water and ethyl acetate. The organic phase was washed with sodium sulfite, water, brine, dried (MgSO4), and concentrated in vacuo. The residue was chromatographed on silica gel to give 437 mg (86%) of 5-(4-fluorophenyl)-6-[4-(methylsulfonyl)phenyl]spiro[2.4]hept-5-ene as a colorless solid: mp 140.5°-142.0° C.; NMR (CDCl3) δ 0.69 (s, 4H), 2.92 (s, 4H), 3.04 (s, 3H), 6.93 (t, J=9 Hz, 2H), 7.10 (dd, J=5 and 9 Hz, 2H), 7.32 (d, J=8 Hz, 2H), 7.76 (d, J=8 Hz, 2H). HRMS. Calc'd for C20H19FO2S: 342.1090. Found: 342.1126. Anal, Calc'd for C20H19FO2S: C, 70.15; H, 5.59; F, 5.55; S, 9.36. Found: C, 70.10; H, 5.69; F, 5.50; S, 9.60.

Workup

  1. concentrationconcentrated in vacuo
  2. custompartitioned between water and ethyl acetate
  3. washThe organic phase was washed with sodium sulfite, water, brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customThe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-a1d8075f39e4436f9b8018de3654109c
Source dataset
uspto-grants-1997_11
Patent number
US05684195

Reaction notes

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