Phenyl vinyl sulfone → 6-Benzenesulfonyl-8-benzyl-1-phenyl-8-aza-bicyclo[3.2.1]oct-3-en-2-one

HRID 1244034Notes

Reaction equation

HRID 1244034 reaction equation
[Br-].[C:2]1([CH2:8][N+:9]2[CH:14]=[CH:13][CH:12]=[C:11]([OH:15])[C:10]=2[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:22]1([S:28]([CH:31]=[CH2:32])(=[O:30])=[O:29])[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>CO.C1(C=CC(O)=CC=1)O>[C:22]1([S:28]([CH:31]2[CH2:32][C:10]3([C:16]4[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=4)[N:9]([CH2:8][C:2]4[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=4)[CH:14]2[CH:13]=[CH:12][C:11]3=[O:15])(=[O:30])=[O:29])[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

Participants

5

Reactant 2

HCID 79664Phenyl vinyl sulfoneHCID 21931695N-benzyl-3-hydroxy-2-phenylpyridinium bromide

Product 1

HCID 219318066-Benzenesulfonyl-8-benzyl-1-phenyl-8-aza-bicyclo[3.2.1]oct-3-en-2-oneYield 64%

Reagents, catalysts & solvents 2

HCID 785HydroquinoneCatalystHCID 887MethanolSolvent

Procedure

To 7.35 gm (21.5 mmol) 1-phenylmethyl-2-phenyl-3-hydroxypyridinium bromide in 20 ml of methanol was added 8.69 gm Amberlyst AG1-X8 resin —OH form 20–40 mesh. The mixture was stirred for a short period and then filtered and the resin washed with methanol. The solvent was removed in vacuo. The solid residue was taken up in toluene (150 ml) and treated with 50 mg of hydroquinone and 6.84 gm (37.1 mmol) phenyl vinylsulfone. The reaction mixture was heated under reflux for 18 hours and then cooled to room temperature. The solvent was removed in vacuo and the residue was chromatographed on silica gel eluting with 8:2/hexane:ethyl acetate to afford 5.87 gm (64%) of a light yellow solid. 1H NMR (CDCl3, 400 MHz) δ 7.71–7.61 (m, 5H), 7.46 (t, 2H, J=8 Hz), 7.37–7.23 (m, 8H), 6.84 (dd, 1H), J=9 Hz, J=5 Hz), 6.20 (d, 1H, J=9 Hz), 4.22 (d, 1H, J=5 Hz), 3.63 (d, 1H, J=14 Hz), 3.54 (dd, 1H, J=9 Hz, J=4 Hz), 3.40 (d, 1H, J=13 Hz), 2.80 (dd, 1H, J=15 Hz, J=3 Hz), 2.53 (dd, 1H, J=15 Hz, J=5 Hz) ppm. 13C NMR (CDCl3, 125 MHz) δ 196.9, 144.9, 138.3, 138.0, 137.7, 134.3, 130.9, 129.9, 129.8, 129.5, 129.2, 129.2, 129.0, 129.0, 128.9, 128.7, 128.2, 128.1, 127.9, 75.1, 66.3, 57.9, 49.1, 38.1 ppm. Mass spectrum APCI m/z 430 (p+1).

Workup

  1. filtrationfiltered
  2. washthe resin washed with methanol
  3. customThe solvent was removed in vacuo
  4. temperatureThe reaction mixture was heated
  5. temperatureunder reflux for 18 hours
  6. customThe solvent was removed in vacuo
  7. customthe residue was chromatographed on silica gel eluting with 8:2/hexane

Sources & evidence

ORD record
ord-3f2a9d09b81543169f58bdaac4a8bd78
Source dataset
uspto-grants-2006_10
Patent number
US07119207B2

Reaction notes

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