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

HRID 275483Notes

Reaction equation

HRID 275483 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-9f1659dce5be497ebef6d6ba0554bcea
Source dataset
uspto-grants-1995_02
Patent number
US05393790

Reaction notes

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