Pyrrolizinium, 1,2,3,5,6,7-hexahydro-, perchlorate → 7a-(4-methyl-3-pyridinyl)-hexahydro-1H-pyrrolizine
Reaction equation
I[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][C:7]=1[CH3:8].[Li]C(C)(C)C.Cl([O-])(=O)(=O)=O.[CH2:19]1[C:26]2[CH2:25][CH2:24][CH2:23][N+:22]=2[CH2:21][CH2:20]1>CCOCC.CCCCC>[CH3:8][C:7]1[CH:6]=[CH:5][N:4]=[CH:3][C:2]=1[C:26]12[CH2:25][CH2:24][CH2:23][N:22]1[CH2:21][CH2:20][CH2:19]2Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- -95 °C
Procedure
3-Iodo-4-methylpyridine (330 mg, 3.10 mmol) was dissolved in Et2O and cooled to -95° C. A solution of t-BuLi (1.7M in pentane, 4.0 ml, 6.80 mmol) in pentane was added dropwise. 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate (960 mg, 4.60 mmol) was added, and the reaction mixture was allowed to warm to -10° C. with stirring for 2 hours. The cold bath was removed, 2N HCl was added, and the phases were separated. The aqueous phase was basified with 15% NaOH and extracted with CH2Cl2 (2×). The CH2Cl2 fractions were combined, dried (MgSO4) and concentrated, and the residue was chromatographed (silica gel; CHCl3 /MeOH, 99:1) to afford the title compound as an oil (41 mg, 6%): 1H NMR (CDCl3, 300 MHz) δ1.54-1.69 (m, 2H), 1.77-1.89 (m, 2H), 1.93-2.11 (m, 4H), 2.41 (s, 3H), 2.69-2.77 (m, 2H), 3.08-3.15 (m, 2H), 7.02 (d, J=4.8 Hz, 1H), 8.32 (d, J=4.8 Hz, 1H), 9.06 (s, 1H); MS (CI/NH3) m/z: 203 (M+H)+.
Workup
- temperatureto warm to -10° C.
- customThe cold bath was removed
- addition2N HCl was added
- customthe phases were separated
- extractionextracted with CH2Cl2 (2×)
- dry with materialdried (MgSO4)
- concentrationconcentrated
- customthe residue was chromatographed (silica gel; CHCl3 /MeOH, 99:1)
Sources & evidence
- ORD record
- ord-25cc9381e06f48dab75a6ffa0b61c21d
- Source dataset
- uspto-grants-1998_03
- Patent number
- US05733912
Reaction notes
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