Réaction #529587

Équation de réaction

oxygen

2,2'-dipyridyl disulfide

triphenylphosphine

15-methyl-PGF2α

→

(15S)-15-methyl PGF2α

Solvants

—

ice water sodium bicarbonate

ethyl acetate

EtOAc hexane

xylene

Conditions de réaction

Traitement

1. 1
   Autreat 25° C
2. 2
   workup.ADDITIONThe mixture is diluted with 150 ml
3. 3
   Températureat reflux for 3 hr
4. 4
   AutreThe xylene is removed by evaporation at reduced pressure
5. 5
   Autreto afford a residue which
6. 6
   Extractionextracted thoroughly with ethyl acetate
7. 7
   ExtractionThe ethyl acetate extract
8. 8
   Lavageis washed with brine
9. 9
   Concentrationconcentrated

Mode opératoire

A solution of 15-methyl-PGF2α (185 mg.) in 2.5 ml. of an anhydrous, oxygen-free xylene containing 2,2'-dipyridyl disulfide (165 mg.) and triphenylphosphine (196 mg.) is stirred under nitrogen for 2.5 hr. at 25° C. The mixture is diluted with 150 ml. of xylene and heated at reflux for 3 hr. TLC (80 percent EtOAc/hexane) shows essentially a single, less polar product. The xylene is removed by evaporation at reduced pressure to afford a residue which is diluted with ice/water/sodium bicarbonate and ethyl acetate and extracted thoroughly with ethyl acetate. The ethyl acetate extract is washed with brine, dired over anhydrous sodium sulfate and concentrated to afford a residue of (15S)-15-methyl PGF2α , 1,9-lactone. The residue is purified by chromatography on 50 g. of neutral silica packed with 10 percent acetone/methylene chloride and eluted (5 ml. fractions) with 200 ml. of 10 percent acetone/methylene chloride, 1500 ml. of 20 percent acetone/methylene chloride and 1000 ml. of 35 percent acetone/methylene chloride.

Source