Réaction #334884

Équation de réaction

triphenylphosphine

2,2'-dipyridyldisulfide

3-benzylamino-2-(1-hydroxyethyl)-5-trimethylsilyl-4-pentinic acid phenylthioester

potassium hydroxide

hydrochloric acid

→

1-benzyl-4-ethynyl-3-(1-hydroxyethyl)-2-azetidinone

Solvants

acetonitrile

THF

Conditions de réaction

Traitement

1. 1
   Extractionwas extracted six times with ethyl acetate
2. 2
   SéchageThe extract was dried with anhydrous magnesium sulfate
3. 3
   Concentrationconcentrated
4. 4
   workup.ADDITIONThere was added 250 ml of acetonitrile to the concentrated solution
5. 5
   workup.ADDITIONwas added dropwise for 40 minutes
6. 6
   workup.STIRRINGwhile vigorously stirring
7. 7
   Températurewith heating
8. 8
   Températureunder reflux
9. 9
   TempératureAfter the solution was further heated
10. 10
    Températureunder reflux for 1 hour
11. 11
    Autrethe obtained reaction mixture
12. 12
    Concentrationwas concentrated
13. 13
    Autrefollowed by purification with 50 g of silica-gel column-chromatography (eluent; methylene chloride→diethyl ether)

Mode opératoire

There was dissolved 2.054 g (5.0 mmol) of 3-benzylamino-2-(1-hydroxyethyl)-5-trimethylsilyl-4-pentinic acid phenylthioester in 40 ml of THF, to which 3 ml of 4 N potassium hydroxide was added and the mixture was stirred at room temperature for 3 hours. The reaction mixture was neutralized with 2 N hydrochloric acid and was extracted six times with ethyl acetate while conducting salting-out. The extract was dried with anhydrous magnesium sulfate and concentrated. There was added 250 ml of acetonitrile to the concentrated solution, and then 1.57 g (60 mmol) of triphenylphosphine was added, to which 1.32 g (6.0 mmol) of 2,2'-dipyridyldisulfide in 50 ml of acetonitrile was added dropwise for 40 minutes while vigorously stirring with heating under reflux. After the solution was further heated under reflux for 1 hour, the obtained reaction mixture was concentrated, followed by purification with 50 g of silica-gel column-chromatography (eluent; methylene chloride→diethyl ether) and then with 50 g of silica-gel column-chromatography (eluent;hexane:diethyl ether=1:4) to give 801 mg of a trans-form and 62 mg of a cis-form of 1-benzyl-4-ethynyl-3-(1-hydroxyethyl)-2-azetidinone.

Source