Total synthesis of insect sex pheromones: recent improvements based on iron-mediated cross-coupling chemistry

• Eric Gayon,
• Guillaume Lefèvre,
• Olivier Guerret,
• Adrien Tintar and
• Pablo Chourreu

Beilstein J. Org. Chem. 2023, 19, 158–166, doi:10.3762/bjoc.19.15

• economy methodologies. The synthesis of the sex pheromone of the horse-chestnut leaf miner (Cameraria ohridella), (8E,10Z)-tetradecadienal (1, Scheme 1) perfectly illustrates this issue: the main synthetic pathways reported in the literature until now (Svatoš, 1999 [7]; Francke, 2002 [8], Grodner, 2009 [9

• synthetic procedures applied to obtain a variety of insect pheromones. The present report summarizes the recent progresses made in insect sex pheromone synthetic applications in our group, with a particular focus on the quest for non-toxic and sustainable catalytic platforms developed in the iron-catalyzed

• linkage of several insect pheromones. Cahiez paved the way of this strategy in 2008, showing that (E)-dodeca-9,11-dien-1-yl acetate (2), the sex pheromone of red bollworm moth (Diparopsis castanea), which contains a terminal diene, could be obtained at a laboratory scale (ca. 200 mg) by means of iron

1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures

• Bram Ryckaert,
• Ellen Demeyere,
• Frederick Degroote,
• Hilde Janssens and
• Johan M. Winne

Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12

• synthesis starts from a carbonyl compound, wherein an aldehyde can undergo ‘umpolung’ into a cis-vinyl anion equivalent via a 1,3-dithiolane-to-1,4-dithiane rearrangement (Scheme 10b). The potential of the method is demonstrated by the synthesis of (Z)-9-tricosene or muscalure (59), which is the natural sex

• pheromone of the common house fly [58]. The aldehyde 55 is converted into a vinyl anion equivalent 57 in two high yielding and operationally simple steps. The alkylation of this dihydrodithiin intermediate proceeds extremely smoothly, yielding the 1,4-dithiane-tethered version of the target molecule (58). A

Synthesis of disparlure and monachalure enantiomers from 2,3-butanediacetals

• Adam Drop,
• Hubert Wojtasek and
• Bożena Frąckowiak-Wojtasek

Beilstein J. Org. Chem. 2020, 16, 616–620, doi:10.3762/bjoc.16.57

• semiochemicals. They have been frequently found as pheromones in lepidopteran species of the families Noctuidae, Arctiidae, Lymantridae, Geometridae and Erebidae [1]. (3Z,9Z)-6S,7R-Epoxyheneicosa-3,9-diene, a constituent of the female sex pheromone of the moth Tetanolita mynesalis (Erebidae) [2] is a

• ) and the nun moth (Lymantria monacha). The sex pheromone of the gypsy moth contains (+)-disparlure (1, (7R,8S)-7,8-epoxy-2-methyloctadecane) [10]. The pheromone blend of the nun moth contains (−)-disparlure (3, (7S,8R)-7,8-epoxy-2-methyloctadecane), (+)-monachalure (2, (7R,8S)-cis-7,8-epoxyoctadecane

Two antibacterial and PPARα/γ-agonistic unsaturated keto fatty acids from a coral-associated actinomycete of the genus Micrococcus

• Amit Raj Sharma,
• Enjuro Harunari,
• Naoya Oku,
• Nobuyasu Matsuura,
• Agus Trianto and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2020, 16, 297–304, doi:10.3762/bjoc.16.29

• eggplant calyx induces apoptosis in human ovarian cancer cells, leading to cell death [33]. One example of a keto fatty acid from the animal kingdom is (E)-9-oxo-2-decenoic acid, a sex pheromone found in royal jelly. Queen honey bees use this fatty acid to control the activity of worker bees [34]. (E)-7

Mechanistic investigations on multiproduct β-himachalene synthase from Cryptosporangium arvum

• Jan Rinkel and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2019, 15, 1008–1019, doi:10.3762/bjoc.15.99

• verbenol, for which synergistic effects were observed compared to the single compounds [2]. Also the sex pheromone of the cranberry white grub Phyllophaga anxia was identified as a compound mixture, consisting of L-valine methyl ester and L-isoleucine methyl ester at a 3:1 ratio [3]. Moreover, if there is

Biosynthesis of α-pyrones

• Till F. Schäberle

Beilstein J. Org. Chem. 2016, 12, 571–588, doi:10.3762/bjoc.12.56

• (Figure 1) [7]. α-Pyrones have also been shown to be HIV protease [8][9][10] and selective COX-2 inhibitors [11][12], and further, signaling functions were attributed to them. Already in the 1990s an unusual dialkyl-substituted α-pyrone (supellapyrone, 7) was detected to be the cockroach sex pheromone [13

Asymmetric total synthesis of a putative sex pheromone component from the parasitoid wasp Trichogramma turkestanica

• Danny Geerdink,
• Jeffrey Buter,
• Teris A. van Beek and
• Adriaan J. Minnaard

Beilstein J. Org. Chem. 2014, 10, 761–766, doi:10.3762/bjoc.10.71

• Wageningen, The Netherlands 10.3762/bjoc.10.71 Abstract Virgin females of the parasitoid wasp Trichogramma turkestanica produce minute amounts of a sex pheromone, the identity of which has not been fully established. The enantioselective synthesis of a putative component of this pheromone, (6S,8S,10S

• of 4.4%. Keywords: asymmetric catalysis; copper; deoxypropionates; natural products; sex pheromone; Trichogramma turkestanica; Introduction Communication by means of pheromones is common in many animal species. For instance, many insects secrete air-borne volatiles to attract a mate for generating

• offspring [1][2]. In 2005, one of us reported the isolation and partial characterization of the putative sex pheromone of Trichogramma turkestanica, a parasitoid wasp [3]. These wasps, belonging to the large Trichogrammatidae family, are minute in size (0.5 mm, 8 µg adult weight) as well as morphologically

Organocatalytic tandem Michael addition reactions: A powerful access to the enantioselective synthesis of functionalized chromenes, thiochromenes and 1,2-dihydroquinolines

• Chittaranjan Bhanja,
• Satyaban Jena,
• Sabita Nayak and
• Seetaram Mohapatra

Beilstein J. Org. Chem. 2012, 8, 1668–1694, doi:10.3762/bjoc.8.191

• compounds having antiviral, antitumor, antimicrobial, antidiabetic, sex-pheromone, diuretic, anticoagulant, anti-anaphylatic and many more activities [1][2][3][4][5][6][7][8][9]. Some representative molecules of these structural motifs are shown in Figure 1 [9][10][11][12][13][14][15][16][17][18][19][20][21

On the proposed structures and stereocontrolled synthesis of the cephalosporolides

• Sami F. Tlais and
• Gregory B. Dudley

Beilstein J. Org. Chem. 2012, 8, 1287–1292, doi:10.3762/bjoc.8.146

• norhalichondrin [13][14]. Spiroketal-containing pheromones are especially prominent in insect communication, with the spiroketal stereochemistry often relaying important information [15]. For example, the R-enantiomer of the olive-fly sex pheromone is attractive to males, while the S-enantiomer attracts females

• (Figure 1). Chalcogran, a sex pheromone secreted by the male bark beetle, is isolated from natural sources as a mixture of diastereomers. However, Byers et al showed that the spiroketal (2R,5R)-isomer induces the strongest responses from both females and males [16]. In such cases it is interesting to

Stereoselective synthesis of trans-fused iridoid lactones and their identification in the parasitoid wasp Alloxysta victrix, Part II: Iridomyrmecins

• Robert Hilgraf,
• Nicole Zimmermann,
• Lutz Lehmann,
• Armin Tröger and
• Wittko Francke

Beilstein J. Org. Chem. 2012, 8, 1256–1264, doi:10.3762/bjoc.8.141

• that, the cis-fused nepetalactone 15 and diastereomers thereof are typical components of many species of the plant genus Nepeta [22][23]. Along with the corresponding hemiacetal 16, which shows (1R)-configuration, 15 is also a most important sex pheromone of aphids [24] (Figure 8). Nevertheless

• Iridomyrmex humilis [28]. More recently, (1S,2R,3S)-dolichodial (18) has been identified as an electrophysiologically active volatile released from the rosy apple aphid Dysaphis plantaginea oviparae and has been discussed apart from 15 and 16 as a possible third component of the aphid sex pheromone [29

Stereoselective synthesis of trans-fused iridoid lactones and their identification in the parasitoid wasp Alloxysta victrix, Part I: Dihydronepetalactones

• Nicole Zimmermann,
• Robert Hilgraf,
• Lutz Lehmann,
• Daniel Ibarra and
• Wittko Francke

Beilstein J. Org. Chem. 2012, 8, 1246–1255, doi:10.3762/bjoc.8.140

• repellent to the aphid-parasitoid, Aphidius, by warning the primary parasitoid of the presence of the hyperparasitoid [5]. The prenyl-homologue of 1, geranylacetone (5), seems to be a component of the sex pheromone of Alloxysta victrix [6]. In addition, GC/MS of cephalic secretions of both sexes showed a

• secretions of the abdominal defense glands of the rove beetle Creophilus maxillosus [39]. Interestingly, the structure of a' is relatively close to that of nepetalactone 7 and lactol 8, the sex pheromone of the grain aphid S. avenae [13] which keeps the second level in the investigated tetratrophic system

Volatile organic compounds produced by the phytopathogenic bacterium Xanthomonas campestris pv. vesicatoria 85-10

• Teresa Weise,
• Marco Kai,
• Anja Gummesson,
• Armin Troeger,
• Stephan von Reuß,
• Silvia Piepenborn,
• Francine Kosterka,
• Martin Sklorz,
• Ralf Zimmermann,
• Wittko Francke and
• Birgit Piechulla

Beilstein J. Org. Chem. 2012, 8, 579–596, doi:10.3762/bjoc.8.65

• produced by chain shortening of 13-methyltetradecanoyl-SCoA. Further steps during β-oxidation will afford III via IV. With the exception of 8-methylnonan-2-one (24), an important component of the female-produced sex pheromone of the desert spider Agelenopsis aperta [51], no significant biological