An electron transfer model for PGI biosynthesis

✍ Scribed by Ned A. Porter; Robert C. Mebane

• Publisher: Elsevier Science
• Year: 1982
• Tongue: French
• Weight: 231 KB
• Volume: 23
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)87323-2

✦ Synopsis

A biomimetic conversion of the endoperoxide lb to prostacyclin (PGI?) analogs is achieved with the aid of ferrous ion catalysis. Several mechanisms have been suggested for the biosynthesis of PG12 (2a) from PGH2 (la)(l-5) but little has been presented. have been limited by experimental evidence bearing directly on the question of mechanism Studies designed to mimic the enzymatic conversion of PGH2 to PG12 the quantity of PGH2 available and also by the complexity of product Sir: a R,:(CH2)3COOH, R2=H, R3 =CH'CH-CHOH-CSHII b R,=H, R2=Ph,Rg'H mixtures generally obtained. We chose the simple system (lb) for studies of this conversion since (a) we could prepare this compound in 100 mg quantities by chemical synthesis and, (b) we anticipated that the removal of the RS substituent on the endoperoxide nucleus would potentially simplify the product mixtures obtained in biomimetic studies. We report here on the reaction of (1) with one electron reducing agents such as Fe(2+). Our results support the notion that conversion of the PGH2 endoperoxide nucleus to the PGI2 structure may be catalyzed by an electron transfer shuttle mechanism. OR2 40 R=H b R=THP la R,=R2'H b R,= R2'Ac F R,=THP,R2=Ac 101, 4319.