Optimization of insecticidal triterpene derivatives by biomimetic oxidations with hydrogen peroxide and iodosobenzene catalysed by MnIII and FeIII porphyrin complexes.

Optimization of insecticidal triterpene derivatives by biomimetic oxidations with hydrogen peroxide and iodosobenzene catalysed by MnIII and FeIII porphyrin complexes. Chem Biodivers. 2020 Jul 09;: Authors: Mazoir N, Benharref A, Vaca L, González-Coloma A, Reina M Abstract Semisynthetic functionalized triterpenes ( 1 , 3β-acetoxy-8a,9a-epoxy-4a,14a-dimethyl-5a-cholestane; 2 , 4α,14α-dimethyl-5α-cholest-8-ene-3,7,11-trione; 3 , 4α,14α-dimethyl-5α-cholesta-7,9-dien-3-one and 4 , 3β-acetoxy-4a,14a-dimethyl-5a-cholest-8-ene), previously prepared from 31-norlanostenol, a natural insecticide isolated from Euphorbia officinarum latex, have been subjected to oxidation with hydrogen peroxide (H 2 O 2 ) and iodosobenzene (PhIO) catalyzed by porphyrin complexes (cytochrome P-450 models) in order to obtain optimized derivatives with high regioselectivity. The main transformations were epoxidation of the double bonds and hydroxylations of non-activated C-H groups and the reaction products were  3β-acetoxy-4α,14α-dimethyl-5α-cholesta-7,11-dien-25-ol ( 5 , 59 %), 25-hydroxy-4α,14α-dimethyl-5α-cholest-8-ene-3,7,11-trione ( 6, 60 %), 7,8-epoxy-4α,14α-dimethyl-5α-cholest-9-en-3-one ( 7, 22 %), 8-hydroxy-4α,14α-dimethyl-5α-cholest-9-ene-3,7-dione ( 8 , 16 %), 7,8-epoxy-12-hydroxy-4α,14α-dimethyl-5α-cholest-9-en-3-one ( 9, 16%), and 1 (26 %), respectively. We also investigated the insect ( Myzus persicae , Rhopalosiphum padi an...
Source: Chemistry and Biodiversity - Category: Biochemistry Authors: Tags: Chem Biodivers Source Type: research