Sodium Sulfite → Tert-butyl 6-(4-chlorophenyl)-1-methyl-7-oxa-3-azabicyclo[4.1.0]heptane-3-carboxylate

HRID 1888128Notes

Reaction equation

HRID 1888128 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][C:9]=2[CH3:21])=[CH:4][CH:3]=1.C1C=C(Cl)C=C(C(OO)=[O:30])C=1.S([O-])([O-])=O.[Na+].[Na+]>C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]23[O:30][C:9]2([CH3:21])[CH2:10][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:12][CH2:13]3)=[CH:4][CH:3]=1

Participants

5

Conditions

Temperature
0 °C

Procedure

A solution of tert-butyl 4-(4-chlorophenyl)-3-methyl-5,6-dihydropyridine-1(2H)-carboxylate (1.09 g, 3.54 mmol) in methylene chloride (15 mL) was cooled to 0° C. and treated dropwise with a solution of m-CPBA (1.111 g, 4.96 mmol) in methylene chloride (15 mL). The reaction was stirred at 0° C. for 1 hour, then allowed to slowly warm to room temperature and stirred overnight. The mixture was cooled to 0° C., treated with saturated aqueous sodium sulfite (20 mL), and stirred for 1 hour. The layers were separated, and the organic phase was washed once with water, 3× with saturated sodium carbonate, once with water, and once with brine, dried over sodium sulfate, and concentrated in vacuo. The residue was purified over a 120 g silica gel column, eluting at 85 mL/min with a 0% to 17% ethyl acetate/hexanes gradient followed by 17% ethyl acetate/hexanes to yield the title compound as a colorless oil. MS (ESI+)=268.2 (M−tert-Bu)+, 250.1 (M−tert-BuO)+.

Workup

  1. temperatureto slowly warm to room temperature
  2. stirringstirred overnight
  3. temperatureThe mixture was cooled to 0° C.
  4. stirringstirred for 1 hour
  5. customThe layers were separated
  6. washthe organic phase was washed once with water, 3× with saturated sodium carbonate, once with water
  7. dry with materialonce with brine, dried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified over a 120 g silica gel column
  10. washeluting at 85 mL/min with a 0% to 17% ethyl acetate/hexanes gradient

Sources & evidence

ORD record
ord-9061af68625f4a5e899c30099bca30d8
Source dataset
uspto-grants-2013_08
Patent number
US08501782B2

Reaction notes

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