Iron(III)picolinate-induced oxygenation and subsequent rearrangement of triterpenoid derivatives with hydrogen peroxide.
The reaction of oleanane triterpenoid 1b with a FeIII(PA; picolinate)3/H2O2/MeCN system (reagent system A), a simple model system for mono-oxygenase, gave the 11 alpha-hydroxyl derivative 3 as major product, along with 11-oxo derivative 4 and 12-oxo derivative 6. The reaction of lupane triterpenoid 2b with reagent system A gave only oxidative rearrangement compounds, (20R)-aldehyde 8 and (20S)-aldehyde 9 were epimeric isomers. Then, we have found that iron(III) picolinate complex, FeIII(PA)3 is efficient in effecting the rearrangement of triterpenoid epoxides 5 and 7 into the corresponding carbonyl compounds, 6, 8 and 9 with 1,2-shift of the hydride.
Okamoto
I
I
Showa College of Pharmaceutical Sciences, Tokyo, Japan.
Takeya
T
T
Kagawa
Y
Y
Kotani
E
E
D000107:Acetylation; D000970:Antineoplastic Agents / Q000737:chemistry; D002723:Chlorobenzoates; D005290:Ferric Compounds / Q000737:chemistry; D006861:Hydrogen Peroxide; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008745:Methylation; D016877:Oxidants; D010084:Oxidation-Reduction; D010848:Picolinic Acids / Q000737:chemistry*; D019441:Plant Epidermis / Q000737:chemistry; D010944:Plants / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D014315:Triterpenes / Q000737:chemistry*; D000094062:Betulinic Acid
D000970:Antineoplastic Agents; D002723:Chlorobenzoates; D005290:Ferric Compounds; D006861:Hydrogen Peroxide; D007202:Indicators and Reagents; D016877:Oxidants; D010848:Picolinic Acids; D014315:Triterpenes; C002503:betulin; D000094062:Betulinic Acid; C000433:3-chloroperbenzoic acid; C030614:picolinic acid