Реакция #3386

Уравнение реакции

HCl

tBuLi

2,3-dichloro-5-iodopyridine

1,2,3,5,6,7-hexahydropyrrolizinium perchlorate

→

oil

Выход 54.3%

7a-(5,6-dichloro-3-pyridinyl)-hexahydro-1H-pyrrolizine

Выход 54.3%

Растворители

pentane

Et2O

Условия реакции

Обработка

1. 1
   Другоеprecooled to -100° C
2. 2
   workup.STIRRINGto stir for 20 minutes at -100° C.
3. 3
   Другоеthe cold bath was removed
4. 4
   ТемператураAfter warming to ambient temperature
5. 5
   workup.ADDITIONthe reaction mixture was poured over EtOAc
6. 6
   Другоеthe phases were separated
7. 7
   Экстракцияextracted with CH2Cl2 (2×)
8. 8
   Сушкаdried (MgSO4)
9. 9
   Концентрированиеconcentrated
10. 10
    Другоеthe residue was chromatographed (silica gel; CHCl3 /MeOH, 99.5:0.5)

Методика

A solution of 1.7M tBuLi (4.7 mL, 8.0 mmol) in pentane was added to 2,3-dichloro-5-iodopyridine (from step 8a, 1.0 g, 3.65 mmol) in Et2O (15 mL) precooled to -100° C. After stirring for 2 minutes, 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate (1.5 g, 7.3 mmol) was added, and the reaction mixture was allowed to stir for 20 minutes at -100° C. then gradually warm to -20° C. A solution of 2N HCl was added, and the cold bath was removed. After warming to ambient temperature, the reaction mixture was poured over EtOAc and the phases were separated. The aqueous phase was basified with 15% NaOH solution and extracted with CH2Cl2 (2×). The CH2Cl2 phases were combined, dried (MgSO4), concentrated and the residue was chromatographed (silica gel; CHCl3 /MeOH, 99.5:0.5) to afford a light yellow oil (510 mg, 54%). MS (CI/NH3) m/e: 257 (M+H)+. 1H NMR (CDCl3, 300 MHz) δ1.59-1.71 (m, 2H), 1.80-2.08 (m, 6H), 2.64-2.72 (m, 2H), 3.11-3.20 (m, 2H), 7.99 (d, J=2.2 Hz, 1H), 8.36 (d, J=2.2 Hz, 1H).

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