Novel Lactone-Based Insecticides and Drosophila suzukii Management: Synthesis, Potential Action Mechanisms and Selectivity for Non-Target Parasitoids.

Drosophila suzukii, an invasive insect pest, poses a significant threat to various fruit crops. The use of broad-spectrum insecticides to control this pest can reduce the effectiveness of biological control agents, such as the parasitoid Trichopria anastrephae. Here, we evaluated the toxicity of newly synthesized lactone derivatives on D. suzukii and their selectivity towards T. anastrephae. We used in silico approaches to identify potential targets from the most promising molecules in the D. suzukii nervous system and to understand potential differences in susceptibilities between D. suzukii and its parasitoid. Of the nine molecules tested, (rac)-8 and compound 4 demonstrated efficacy against the fly. Exposure to the estimated LC90 of (rac)-8 and compound 4 resulted in a mortality rate of less than 20% for T. anastrephae without impairing the parasitoid's functional parasitism. The in silico predictions suggest that (rac)-8 and compound 4 target gamma amino butyric acid (GABA) receptors and transient receptor potential (TRP) channels of D. suzukii. However, only the reduced interaction with TRP channels in T. anastrephae demonstrated a potential reason for the selectivity of these compounds on the parasitoid. Our findings suggest the potential for integrating (rac)-8 and compound 4 into D. suzukii management practices.

Characterization of stereoisomeric 5-(2-nitro-1-phenylethyl)furan-2(5H)-ones by computation of 1 H and 13 C NMR chemical shifts and electronic circular dichroism spectra.

In the present work, we describe the preparation of two diastereomers from the enantioselective Michael addition of furan-2(5H)-one to (E)-(2-nitrovinyl)benzene catalyzed by a dinuclear Zn-complex. The relative configurations of the diastereomeric products were assigned by comparing nuclear magnetic resonance (NMR) experimental chemical shift data with those computed by density functional theory (DFT) methods. Corrected mean absolute error (CMAE) and CP3 analyses were used to compare the data sets. The absolute configuration of each diastereomer was initially assigned by analysis of electronic circular dichroism (ECD) data, which was consistent with that of the known X-ray crystallographic structure of the product of a related reaction, namely, (R)-5-((R)-1-(4-chlorophenyl)-2-nitroethyl)furan-2(5H)-one.

Herbicidal activity of isobenzofuranones and in silico identification of their enzyme target.

BACKGROUND: Given the weed resistance to various herbicides with different mechanisms of action, the search for new compounds that are more effective and exhibit low levels of impact to other species in nature has been imperative in the field of the agriculture. For this purpose, 16 phthalides, and furan-2(5H)-one were synthetized and evaluated for their effectiveness as herbicides in seeds of Sorghum bicolor (sorghum), Cucumis sativus (cucumber), and Allium cepa (onion). Furthermore, a preliminary in silico study was carried out to identify the enzyme target of the most active compounds. RESULTS: In the assays with S. bicolor, the mixture rac-(3aR,4R,5S,6S,7S,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one + rac-(3aR,4R,5R,6R,7S,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one (15a + 15b) showed comparable inhibitory activity to (S)-metolachlor, which was used as control herbicide at concentrations ranging from 50 µm to 1000 µm. The developments of the seeds evaluated were altered by all 17 compounds, either stimulating or inhibiting. The best results were presented by compounds 15a, and 15b, either in their pure form or as a mixture. CONCLUSION: The results presented by 15a, and 15b were superior to the activity of the commercial herbicide (S)-metolachlor in the assays with C. sativus, and A. cepa. The in silico study provides strong evidence that the most active compounds bind to strigolactones esterases D14 through the same binding site of (5R)-5-hydroxy-3-methylfuran-2(5H)-one (H3M), which is one of the strigolactones (SLs) cleavage products. © 2019 Society of Chemical Industry.

Computation and structural elucidation of compounds formed via epoxide alcoholysis.

Isobenzofuranones are known for their wide range of biological activities such as fungicide, insecticide, and anticancer. The search for novel bioactive compounds was performed by reaction of epoxide 2 with methanol, ethanol, propan-1-ol, propan-2-ol, and butan-1-ol. The mechanism for the stereoselective and stereospecific epoxide opening with methanol was reasoned by calculating the transition states for the two putative structures (rac)-3a and (rac)-3b. The compound (rac)-3a is the kinetic product as inferred from the lower energies of its transition state (TS1). The 1 H and 13 C nuclear magnetic resonance (NMR) chemical shifts for these two candidate structures were calculated and compared with the experimental data using mean absolute error (MAE) and DP4 analyses. Therefore, the relative stereochemistry of (rac)-3a was established by the mechanism, MAE, and DP4 approaches. The hydroxyl group was acetylated to surpass the problem of signal overlapping of H5 and H6 in the 1 H NMR. The relative stereochemistry of the corresponding ester determined by NMR interpretation was in agreement with the structure of (rac)-3a.