반응 #701295

반응 방정식

cyclopentenone

Lithium

naphthalene

allyl phenyl ether

naphthalene

allyllithium

1-iodo-2-pentyne

tetramethylethylenediamine

→

3-allylcyclopentanone

수율 57.0%

용매

tetrahydrofuran

tetrahydrofuran

tetrahydrofuran

tetrahydrofuran

hexamethylphosphoramide

methanol

반응 조건

후처리

1. 1
   workup.WAITAfter an additional 1.25 hours at room temperature
2. 2
   workup.WAITAfter 5 minutes
3. 3
   온도cooled to -78°
4. 4
   workup.WAITAfter 40 minutes at -78°
5. 5
   workup.STIRRINGAfter rapidly stirring for 15 minutes
6. 6
   기타the organic phase was separated
7. 7
   세척washed successively with aqueous sodium hydroxide, aqueous hydrochloric acid, aqueous sodium thiosulfate, and aqueous sodium chloride
8. 8
   건조After drying over potassium carbonate
9. 9
   기타the solvent was removed under reduced pressure
10. 10
    기타the resulting oil was chromatographed on silica gel

실험 절차

Lithium wire (2.1 g, 303 mmol) in small pieces in 26 ml of dry tetrahydrofuran containing a trace of naphthalene under argon was cooled to -15° and was treated with 3.32 g (24.8 mmol) of allyl phenyl ether in 14 ml of tetrahydrofuran containing a trace of naphthalene, with rapid stirring for 45 minutes. After an additional 1.25 hours at room temperature, 14.7 ml (ca. 6.6 mmol) of the allyllithium solution was added at -15° over 2 minutes to 635 mg (3.3 mmol) of copper iodide in 10 ml of tetrahydrofuran under argon with rapid stirring. After 5 minutes, the dark solution was of lithium diallylcuprate cooled to -78° and 245 mg (3.0 mmol) of cyclopentenone in 2 ml of tetrahydrofuran was added over 2 minutes. After 40 minutes at -78°, 1 ml of tetramethylethylenediamine was added followed 5 minutes later by 3.0 g (15.5 mmol) of 1-iodo-2-pentyne in 10 ml of hexamethylphosphoramide. After 2 additional hours at -78°, 1 ml of methanol was added and the mixture was poured into aqueous ammonium chloride-ammonium hydroxide-ether. After rapidly stirring for 15 minutes, the organic phase was separated and washed successively with aqueous sodium hydroxide, aqueous hydrochloric acid, aqueous sodium thiosulfate, and aqueous sodium chloride. After drying over potassium carbonate, the solvent was removed under reduced pressure and the resulting oil was chromatographed on silica gel using chloroform-hexane to afford 325 mg of 2-pentynyl, 3-allylcyclopentanone (57%).

출처