m-Chloroperbenzoic acid → 6-(3-Nitro-phenyl)-7-oxa-3-aza-bicyclo[4.1.0]heptane-3-carboxylic acid tert-butyl ester

HRID 472473Notes

Reaction equation

HRID 472473 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11]([C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([N+:20]([O-:22])=[O:21])[CH:15]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1C=C(Cl)C=C(C(OO)=[O:31])C=1>ClCCl>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH2:10][C:11]2([C:14]3[CH:19]=[CH:18][CH:17]=[C:16]([N+:20]([O-:22])=[O:21])[CH:15]=3)[CH:12]([O:31]2)[CH2:13]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 15751429Tert-butyl 4-(3-nitrophenyl)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 866483556-(3-Nitro-phenyl)-7-oxa-3-aza-bicyclo[4.1.0]heptane-3-carboxylic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

186 b) To a solution of 4-(3-nitro-phenyl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (0.50 g, 1.6 mmol) in dichloromethane (5 mL) was added m-CPBA 70-75% (0.57 g, 2.3 mmol). The mixture was stirred at room temperature for 18 hours. The reaction was quenched by the addition of saturated aqueous sodium thiosulfate solution followed by saturated aqueous sodium bicarbonate. The mixture was stirred for 1 hour. The mixture was extracted with dichloromethane (3×20 mL). The combined organic layers were dried over magnesium sulfate, filtered and evaporated. The residue was purified via chromatography (silica gel column 40 g and 10%→80% ethyl acetate:hexane solvent gradient). 6-(3-Nitro-phenyl)-7-oxa-3-aza-bicyclo[4.1.0]heptane-3-carboxylic acid tert-butyl ester was isolated as a yellow oil (0.335 g, 64%). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.24 (s, 1H), 8.17 (d, J=7.9 Hz, 1H), 7.70 (d, J=7.8 Hz, 1H), 7.55 (t, J=7.9 Hz, 1H), 4.22-3.98 (m, 1H), 3.90-3.62 (m, 2H), 3.31-3.14 (m, 2H), 2.56-2.46 (m, 1H), 2.25-2.12 (m, 1H), 1.49 (s, 9H). MS=343 (M+Na)+.

Workup

  1. customThe reaction was quenched by the addition of saturated aqueous sodium thiosulfate solution
  2. stirringThe mixture was stirred for 1 hour
  3. extractionThe mixture was extracted with dichloromethane (3×20 mL)
  4. dry with materialThe combined organic layers were dried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was purified via chromatography (silica gel column 40 g and 10%→80% ethyl acetate:hexane solvent gradient)

Sources & evidence

ORD record
ord-c77b4a7438f347b5949ee1ba0399aa6b
Source dataset
uspto-grants-2014_01
Patent number
US08633173B2

Reaction notes

Loading…