Sodium Sulfite → Tert-butyl 6-(4-chlorophenyl)-1-methyl-7-oxa-3-azabicyclo[4.1.0]heptane-3-carboxylate
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]=1Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
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
- temperatureto slowly warm to room temperature
- stirringstirred overnight
- temperatureThe mixture was cooled to 0° C.
- stirringstirred for 1 hour
- customThe layers were separated
- washthe organic phase was washed once with water, 3× with saturated sodium carbonate, once with water
- dry with materialonce with brine, dried over sodium sulfate
- concentrationconcentrated in vacuo
- customThe residue was purified over a 120 g silica gel column
- 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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