Dichloromethane → tert-Butyl 6-Oxa-3-azabicyclo(3.1.0)hexane-3-carboxylate

HRID 252089

Reaction equation

HRID 252089 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]=[CH:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].ClC1C=C(C=CC=1)C(OO)=[O:18].ClCCl>ClCCCl>[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]2[CH:10]([O:18]2)[CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 70297m-Chloroperbenzoic acid2×HCID 5148195tert-Butyl 2,5-dihydro-1H-pyrrole-1-carboxylate

Product 1

HCID 10103880tert-Butyl 6-Oxa-3-azabicyclo(3.1.0)hexane-3-carboxylateYield 71%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

Stir a mixture of 2,5-dihydropyrrole-1-carboxylic acid tert-butyl ester (2 g, 11.8 mmol), 3-chloroperoxybenzoic acid (77%, 3.1 g, 14.2 mmol) and 3-tert-butyl-4-hydroxy-5-methylsulfide (254 mg, 0.7 mmol) in 1,2-dichloroethane (50 mL) at 85° C. for 4 h under nitrogen. Add extra 3-chloroperoxybenzoic acid (77%, 1.16 g, 4.7 mmol) and stir at 85° C. for 5 h. Allow to cool to room temperature and add dichloromethane (120 mL), wash with 5% aqueous sodium bisulfate, then with saturated aqueous sodium hydrogen carbonate and finally with saturated aqueous sodium chloride, dry (magnesium sulfate), concentrate and chromatograph on silica gel, eluting with 0:100 to 40:60 ethyl acetate:cyclohexane to give 6-oxa-3-azabicyclo[3.1.0]hexane-3-carboxylic acid tert-butyl ester (1.55 g, 71%). 1H NMR (400 MHz, CDCl3) δ 3.82 (1H, d, J=13.20 Hz), 3.74 (1H, d, J=12.72 Hz), 3.67 (2H, d, J=3.42 Hz), 3.31 (2H, dd, J=13.45, 5.14 Hz), 1.44 (9H, s).

Workup

  1. stirringstir at 85° C. for 5 h
  2. washwash with 5% aqueous sodium bisulfate
  3. dry with materialwith saturated aqueous sodium hydrogen carbonate and finally with saturated aqueous sodium chloride, dry (magnesium sulfate)
  4. concentrationconcentrate
  5. washchromatograph on silica gel, eluting with 0:100 to 40:60 ethyl acetate

Sources & evidence

ORD record
ord-81f91683b3604389a8c6adac3c43ded9
Source dataset
uspto-grants-2011_01
Patent number
US07868014B2

Linked notes

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