Reacción #674298

Ecuación de reacción

potassium t-butoxide

tert-butyl 4-oxopiperidine-1-carboxylate

hexane

→

tert-butyl 4-methylenepiperidine-1-carboxylate

Rendimiento 94.2%

Disolventes

ether

ether

Condiciones de reacción

Tratamiento posterior

1. 1
   Temperaturaat reflux for 2 hrs
2. 2
   Temperaturato warm to room temperature
3. 3
   workup.STIRRINGstirred at room temperature for 1 h
4. 4
   workup.STIRRINGThe mixture was then stirred
5. 5
   Temperaturaat reflux overnight (16 h)
6. 6
   TemperaturaThe mixture was cooled to room temperature
7. 7
   workup.STIRRINGThe mixture was stirred for 10 min
8. 8
   Filtraciónfiltered
9. 9
   Lavadoeluted with Hexane/EtOAc (100/100 mL)
10. 10
    ConcentraciónThe combined organic solution was concentrated
11. 11
    Otroto give the residue which
12. 12
    Otrowas purified by CombiFlash (100 g silica gel column, EtOAc/Hex=0-30%)

Procedimiento

To a suspension of methyltriphenylphosphonium bromide (36.3 g, 101.6 mmol, 1.35 equiv) in ether (dry, 300 mL) was added potassium t-butoxide (11 g, 98 mmol, 1.3 equiv) in one portion at 0° C. under nitrogen balloon. The mixture was then stirred at reflux for 2 hrs. The hot reaction mixture was cooled to 0° C. with an external ice-bath and then a solution of tert-butyl 4-oxopiperidine-1-carboxylate (15 g, 75.3 mmol, 1.0 equiv) in ether (60 mL) was added dropwise. The mixture was allowed to warm to room temperature and stirred at room temperature for 1 h. The mixture was then stirred at reflux overnight (16 h). The mixture was cooled to room temperature and hexane (300 mL) was added. The mixture was stirred for 10 min, filtered and eluted with Hexane/EtOAc (100/100 mL). The combined organic solution was concentrated to give the residue which was purified by CombiFlash (100 g silica gel column, EtOAc/Hex=0-30%) to afford 14 g (yield 94%) of tert-butyl 4-methylenepiperidine-1-carboxylate as a colorless oil.

Fuente