반응 #3391

반응 방정식

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

nBuLi

diisopropylamine

HCl

2,6-dichloropyridine

→

oil

수율 17.2%

7a-(2,6-dichloro-3-pyridinyl)-hexahydro-1H-pyrrolizine

수율 17.2%

용매

EtOAc

—

hexanes

THF

반응 조건

후처리

1. 1
   workup.STIRRINGstirring
2. 2
   workup.WAITwas continued for 1 hour at -78° C
3. 3
   workup.STIRRINGto stir for 2 hours at -78° C.
4. 4
   온도then warm to ambient temperature
5. 5
   기타The phases were separated
6. 6
   추출extracted with CH2Cl2 (2×)
7. 7
   건조dried (MgSO4)
8. 8
   농축concentrated
9. 9
   기타the residue was chromatographed (silica gel; CHCl3 /MeOH, 98:2)

실험 절차

A solution of 2.5M nBuLi (675 μL, 1.7 mmol) in hexanes was added to diisopropylamine (220 μL, 1.7 mmol) in THF (4.5 mL) at ambient temperature. After 10 minutes of stirring, the reaction mixture was cooled to -78° C., 2,6-dichloropyridine (237 μL, 1.60 mmol) was added neat, and stirring was continued for 1 hour at -78° C. 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate (500 mg, 2.40 mmol) was added, and the reaction mixture was allowed to stir for 2 hours at -78° C. then warm to ambient temperature. A solution of 2N HCl was added, and the mixture was then poured over EtOAc. The phases were separated, and 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, 98:2) to afford a clear oil (70.6 mg, 17%). MS (CI/NH3) m/e: 257/259 (M+H)+. 1H NMR (CDCl3, 300 MHz) δ1.47-1.61 (m, 2H), 1.77-1.90 (m, 2H), 2.10-2.25 (m, 4H), 2.67-2.75 (m, 2H), 3.03-3.11 (m, 2H), 7.19 (d, J=8.5 Hz, 1H), 8.37 (d, J=8.5 Hz, 1H).

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