Ammonium formate → 6-Benzenesulfonyl-8-benzyl-1-phenyl-8-aza-bicyclo[3.2.1]octan-2-one

HRID 1244035Notes

Reaction equation

HRID 1244035 reaction equation
[C:1]1([S:7]([CH:10]2[CH2:16][C:15]3([C:25]4[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=4)[N:17]([CH2:18][C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=4)[CH:11]2[CH:12]=[CH:13][C:14]3=[O:31])(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([O-])=O.[NH4+]>[OH-].[Pd+2].[OH-].CO>[C:1]1([S:7]([CH:10]2[CH2:16][C:15]3([C:25]4[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=4)[N:17]([CH2:18][C:19]4[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=4)[CH:11]2[CH2:12][CH2:13][C:14]3=[O:31])(=[O:9])=[O:8])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 219318066-Benzenesulfonyl-8-benzyl-1-phenyl-8-aza-bicyclo[3.2.1]oct-3-en-2-one

Product 1

HCID 219316456-Benzenesulfonyl-8-benzyl-1-phenyl-8-aza-bicyclo[3.2.1]octan-2-one

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolvent

Procedure

To a 500 ml round bottom flask equipped with nitrogen inlet and condenser was placed 5.87 gm (13.68 mmol) of the 6-Benzenesulfonyl-8-benzyl-1-phenyl-8-aza-bicyclo[3.2.1]oct-3-en-2-one together with 150 ml of methanol, 17.25 gm (273.66 mmol) ammonium formate and 1.95 gm palladium hydroxide. The reaction mixture was heated under reflux for 1.5 hours and then cooled to room temperature. The suspension was filtered through a bed of celite which was then washed with methanol. The combined organics were evaporated in vacuo and the residue was taken up in chloroform and partitioned with saturated aqueous bicarbonate solution. The organics were washed with saturated brine solution and then dried over a bed of sodium sulfate. The mixture was filtered and the filtrate evaporated in vacuo. The residue was chromatographed on silica gel eluting with 8:2/hexane:ethyl acetate to afford 4.04 gm (68%) of an off white solid. 1H NMR (CDCl3, 400 MHz) δ 7.79 (d, 2H, J=7 Hz), 7.66 (t, 1H, J=7 Hz), 7.51 (t, 2H, J=8 Hz), 7.40–7.19 (m, 10H), 3.93 (br.s., 1H), 3.70 (d, 1H, J=15 Hz), 3.62 (t, 1H, J=7 Hz), 3.35 (d, 1H, J=14 Hz), 2.70–2.5 (m, 4H), 1.79–1.70 (m, 1H), 1.55 (br.s., 1H) ppm. Mass spectrum APCI m/z 432 (p+1).

Workup

  1. customTo a 500 ml round bottom flask equipped with nitrogen inlet and condenser
  2. temperatureThe reaction mixture was heated
  3. temperatureunder reflux for 1.5 hours
  4. filtrationThe suspension was filtered through a bed of celite which
  5. washwas then washed with methanol
  6. customThe combined organics were evaporated in vacuo
  7. custompartitioned with saturated aqueous bicarbonate solution
  8. washThe organics were washed with saturated brine solution
  9. dry with materialdried over a bed of sodium sulfate
  10. filtrationThe mixture was filtered
  11. customthe filtrate evaporated in vacuo
  12. customThe residue was chromatographed on silica gel eluting with 8:2/hexane
  13. customethyl acetate to afford 4.04 gm (68%) of an off white solid

Sources & evidence

ORD record
ord-b2db8a3117224b92920270ec4bce00b4
Source dataset
uspto-grants-2006_10
Patent number
US07119207B2

Reaction notes

Loading…