Biocatalysis Applied to the Synthesis of Pheromones

Abstract

The application of biologically derived catalysts to the synthesis of agrochemicals has become increasingly popular in recent years. In most cases, the aim of using a biotransformation is either to introduce chirality into the molecule, to achieve a regioselective functionalization, or to selectively convert a functional group among other groups with similar reactivity. Pheromones, which have recently been commercialized as agrochemicals, are generally used in enantiopure forms with their intentional mixtures. Since they are usually highly effective, only very small quantities are needed to achieve the desired activity. This review, with approximately 200 references covering the period previous to December 2004, describes various efficient means of preparing optically pure pheromones and their precursors with the aid of isolated enzymes and microorganisms serving as catalysts.

Recent advances in the synthesis of insect pheromones: an overview from 2013 to 2022

“…Pheromone synthesis has also benetted from the progress made in methodologies for carbon-carbon coupling reactions. Organometallic compounds such as Grignard reagents, organocuprates, organostannanes, or organozinc reagents are oen employed (e.g., Schemes 3,13,14,[16][17][18]20,and 24). Transition metal catalysts, in particular Cu-and Pd-based complexes, are nowadays indispensable tools for the construction of new bonds (e.g.…”

“…All epoxides were identied from the order Lepidoptera, namely, Lymantria monacha (Lep., Erebidae): 16; L. dispar (Lep., Erebidae): 17; [30][31][32][33] Ectropis obliqua (Lep., Geometridae): 18; [34][35][36][37] Itame argillacearia (Lep., Geometridae): 19; 38 Thyrinteina arnobia (Lep., Geometridae): 20; 39 Lymantria mathura (Lep., Erebidae): 21; 40 and Estigmene acrea (Lep., Erebidae): (9S,10R)-22. 41 The epoxy functional group was obtained by intramolecular nucleophilic displacement reactions (16,17), epoxidation of alkenes with reagents like mCPBA, 34,39 Ti(i-PrO) 4 37,40 (18, 20), or Sharpless asymmetric dihydroxylation (AD-mix), 37,38 followed by intramolecular epoxide ring-closing (18,19). Five epoxides presented an unsaturated aliphatic chain with Z-conguration, obtained by stereoselective alkyne reduction (Lindlar 37,39,41 and P2-Ni 38,40 ) or stereoselective Wittig olenation.…”

“…[10][11][12][13][14][15] Another review by Aleu et al dealt with the use of biocatalysis in pheromone synthesis. 16 The chemistry, including synthetic procedures, of chiral methyl-branched pheromones, 17 lactones used in chemical communication 18 and pheromones of mealybug and scale insects 19 were reviewed as part of a Natural Product Reports special issue on chemical ecology. The identication of insect pheromones from 2001 to 2018 has also recently been revised by Zarbin and Vidal.…”

Embracing Nature’s Catalysts: A Viewpoint on the Future of Biocatalysis

“…Miscellaneous route scouting tools are available or being developed by different companies in order to design more efficient processes for certain types of molecules. A broad portfolio of mostly smaller but high value products ranging from flavor and fragrance compounds, e.g., ambrox, ,, biotin vitamins, , or pheromones , can be manufactured based on biocatalysis. In the future, emerging new and innovating products, like sweeteners, dyestuff, oligosaccharides, functional peptides, nutraceuticals, just to mention a few, will be manufactured using the technological advantage of biocatalytic routes.…”

Synthesis of Pheromones: Highlights from 2002-2004

“…Mori provided comprehensive overviews in 1981 and 1992 [1,2] with a partial update in 2004 [3] and also published articles relating pheromone synthesis to specific topics [4][5][6]. The application of biocatalysis to pheromone synthesis has also been reviewed recently [7].…”