Synthesis and Functionalization of Tertiary Propargylic Boronic Esters by Alkynyllithium-Mediated 1,2-Metalate Rearrangement of Borylated Cyclopropanes.

Implementing the use of alkynyllithium reagents in a stereospecific 1,2-metalate rearrangement-mediated ring opening of polysubstituted cyclopropyl boronic esters provides a variety of tertiary pinacol boranes bearing adjacent tertiary or quaternary carbon stereocenters with high levels of diastereomeric purity. The potential of this strategy was demonstrated through a selection of α- and γ-functionalization of the propargyl boronic esters.

Moving forward with isoprostanes, neuroprostanes and phytoprostanes: where are we now?

Polyunsaturated fatty acids (PUFAs) are essential components in eukaryotic cell membrane. They take part in the regulation of cell signalling pathways and act as precursors in inflammatory metabolism. Beside these, PUFAs auto-oxidize through free radical initiated mechanism and release key products that have various physiological functions. These products surfaced in the early nineties and were classified as prostaglandin isomers or isoprostanes, neuroprostanes and phytoprostanes. Although these molecules are considered robust biomarkers of oxidative damage in diseases, they also contain biological activities in humans. Conceptual progress in the last 3 years has added more understanding about the importance of these molecules in different fields. In this chapter, a brief overview of the past 30 years and the recent scope of these molecules, including their biological activities, biosynthetic pathways and analytical approaches are discussed.

First Total Syntheses of Novel Non-Enzymatic Polyunsaturated Fatty Acid Metabolites and Their Identification in Edible Oils.

Oxidative stress (OS) is an in vivo process leading to free radical overproduction, which triggers polyunsaturated fatty acid (PUFA) peroxidation resulting in the formation of racemic non-enzymatic oxygenated metabolites. As potential biomarkers of OS, their in vivo quantification is of great interest. However, since a large number of isomeric metabolites is formed in parallel, their quantification remains difficult without primary standards. Three new PUFA-metabolites, namely 18-F3t -isoprostane (IsoP) from eicosapentaenoic acid (EPA), 20-F4t -neuroprostane (NeuroP) from docosahexaenoic acid (DHA) and 20-F3t -NeuroP from docosapentaenoic acid (DPAn-3 ) were synthesized by two complementary synthetic strategies. The first one relied on a racemic approach to 18(RS)-18-F3t -IsoP using an oxidative radical anion cyclization as a key step, whereas the second used an enzymatic deracemization of a bicyclo[3.3.0]octene intermediate obtained from cyclooctadiene to pursue an asymmetric synthesis. The synthesized metabolites were applied in targeted lipidomics to prove lipid peroxidation in edible oils of commercial nutraceuticals.

Expansion of the fatty acyl reductase gene family shaped pheromone communication in Hymenoptera.

Fatty acyl reductases (FARs) are involved in the biosynthesis of fatty alcohols that serve a range of biological roles. Insects typically harbor numerous FAR gene family members. While some FARs are involved in pheromone biosynthesis, the biological significance of the large number of FARs in insect genomes remains unclear.Using bumble bee (Bombini) FAR expression analysis and functional characterization, hymenopteran FAR gene tree reconstruction, and inspection of transposable elements (TEs) in the genomic environment of FARs, we uncovered a massive expansion of the FAR gene family in Hymenoptera, presumably facilitated by TEs. The expansion occurred in the common ancestor of bumble bees and stingless bees (Meliponini). We found that bumble bee FARs from the expanded FAR-A ortholog group contribute to the species-specific pheromone composition. Our results indicate that expansion and functional diversification of the FAR gene family played a key role in the evolution of pheromone communication in Hymenoptera.