A methodology to build (E)-β-alkoxy- and (E)-β-aryloxyacrylate moieties from acetate and formate esters promoted by the TiCl/EtN system is presented. The reaction is compatible with a broad range of structural skeletons and elapses through an unusual condensation pathway. Taking into account the obtained results, we propose a plausible mechanism involving a bimetallic titanium intermediate for this type of transformation.

Lachryphagous males of Phortica variegata (Fallén, 1823) are gaining increasing attention in Europe, as they act as vectors of the nematode Thelazia callipaeda Railliet & Henry, 1910, causal agent of thelaziosis, an emergent zoonotic disease. Currently, there are no effective control strategies against the vector, and surveillance and monitoring rely on time-consuming and nonselective sampling methods. Our aim was to improve the knowledge about the population dynamics and the chemical ecology of the species. A total of 5,726 P. variegata flies (96.4% males and 3.6% females, mostly gravid) were collected in field experiments during June–September of 2020 in an oak forest in northern Spain. Our results indicate that 1) by means of sweep netting a significantly higher number of captures were found both around the collector´s body and in the air than at ground level; 2) a positive relationship was detected between the abundance of Phortica flies and temperature, with two significant peaks of abundance at 24 and 33°C; 3) the blend of red wine and cider vinegar was the most attractive bait; 4) yellow traps captured fewer flies compared to black and transparent traps; and 5) a significant reduction toward vinegar and wine was detected in presence of the phenolic monoterpenoid carvacrol. In addition, all the males (n = 690) analyzed by both molecular detection and dissection resulted negative for the presence of T. callipaeda larvae. Overall, these findings provide a better understanding of the vector in terms of monitoring and management strategies.

A study on the electrophile-induced rearrangement of two 15-hydroxygermacranolides, salonitenolide and artemisiifolin, was carried out. These compounds underwent electrophilic intramolecular cyclizations or acid-mediated rearrangements to give sesquiterpene lactones with different skeletons such as eudesmanolides, guaianolides, amorphanolides, or other germacranolides. The cyclization that gives guaianolides can be considered a biomimetic route to this type of sesquiterpene lactones. The use of acetone as a solvent changes the reactivity of the two starting germacranolides to the acid catalysts, with a 4,15-diol acetonide being the main product obtained. The δ-amorphenolide obtained by intramolecular cyclization of this acetonide is a valuable intermediate for accessing the antimalarials artemisinin and its derivatives. Mechanistic proposals for the transformations are raised, and to provide support them, quantum chemical calculations [DFT B3LYP/6-31+G(d,p) level] were undertaken.

The main aim of this work was to identify semiochemicals from the jewel beetle Coraebus undatus (F.) (Coleoptera: Buprestidae) that may aid in the improvement of current monitoring tools. First, HS-SPME collections revealed that individually sampled adults (>7 days old) of both sexes release the spiroacetal 1,7-dioxaspiro[5.5]undecane (olean). Electroantennographic recordings from both sexes exposed to increasing amounts of olean followed a dose-dependent pattern, with females being more responsive than males to the highest amount of the compound (100 µg). In double-choice assays, adults older than seven days were significantly attracted to olean, whereas this attraction was not detected in insects aged less than seven days. Indeed, a repellent effect was observed in young females. Subsequent field trials employing sticky purple prism traps revealed that there were no differences among the number of insects caught in control and olean-baited traps at two different release rates (0.75 and 3.75 mg/day). Interestingly, all the trapped specimens were determined as mated females, regardless of the presence of olean. Overall, these findings provide a basis for unraveling the chemical ecology of the species, although further research is still needed to determine the specific role of this compound within the chemical communication of the species.