Facile and Efficient Syntheses of (11Z,13Z)-Hexadecadienal and Its Derivatives: Key Sex Pheromone and Attractant Components of Notodontidae

Abstract

Syntheses of (11Z,13Z)-hexadecadienal (1), (11Z,13Z)-hexadecadienol (2), (11Z,13Z)-hexadecadien-1-yl acetate (3), and (Z)-13-hexadecen-11-ynal (4) from commercially available starting material 10-bromo-1-decanol are reported. These (Z,Z)-dienes and conjugated en-yne moieties are common in sex pheromone and attractant components for many Notodontide insect pests. The synthetic scheme, using the C10 + C3 + C3 strategy, was mainly based on three key steps: alkylation of lithium alkyne under a low temperature, cis-Wittig olefination of the aldehyde with propylidentriphenylphosphorane, and hydroboration-protonolysis of alkyne. This synthetic route provided (11Z,13Z)-hexadecadienal (1) in a 23.0% total yield via an eight-step sequence, alcohol (2) in a 21.9% total yield, acetate (3) in a 21.4% total yield, and (Z)-13-hexadecen-11-ynal (4) in a 34.7% total yield. This simple strategy provides a new way to achieve syntheses of the key sex pheromones of Notodontide insect pests.

Structural insights into the discrepant synergistic activity of Codlemone and (Z)‐8‐dodecenol towards Grapholita molesta pheromones

“…The discovery of active semiochemicals with new scaffolds was overwhelmingly highlighted. Only a few researchers were interested in optimizing attractants and repellents, and even fewer were involved in the optimization of pheromone synergists 19,66–69 . The present work is an exploration of structure‐based discovery and optimization of more potent insect pheromone synergists.…”

“…Only a few researchers were interested in optimizing attractants and repellents, and even fewer were involved in the optimization of pheromone synergists. 19,[66][67][68][69] The present work is an exploration of structure-based discovery and optimization of more potent insect pheromone synergists. The C10═C11 structure that may act as a functional site contributing heavily to the better synergistic activity of Cod can be taken as a reference factor for prospective screening for OFM pheromone synergists.…”

Synthesis and bioactivity of (13Z,15E)‐octadecadienal: A sex pheromone component from Micromelalopha siversi Staudinger (Lepidoptera: Notodontidae)

“…[30][31][32][33] In addition, (11Z,13Z)-hexadecadienal, together with related derivatives, are the critical sex pheromones and attractants in Notodonfidae. 18,34 (8E,10E)dodecadienyl acetate synergizes the codlemone attraction to male Cydia pomonella, and it is also the sex pheromone of Cydia toreuta (Grote) and Melissopus latiferreanus. [35][36][37] Wittig olefination is an effective protocol to construct the 1,3-diene system of sex pheromone components.…”

“…For instance, the derivatives of (5 Z ,7 E )‐ and (5 E ,7 Z )‐dodecadienol are the active sex pheromone components of pine caterpillars 30–33 . In addition, (11 Z ,13 Z )‐hexadecadienal, together with related derivatives, are the critical sex pheromones and attractants in Notodonfidae 18,34 . (8 E ,10 E )‐dodecadienyl acetate synergizes the codlemone attraction to male Cydia pomonella , and it is also the sex pheromone of Cydia toreuta (Grote) and Melissopus latiferreanus 35–37 …”

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

“…): 42 , 47 Plutella xylostella (Lep., Plutellidae): 43 , 48 Trichoplusia ni (Lep., Noctuidae): 44 , 49 Tortrix viridana (Lep., Tortricidae): 45 , 50 Grapholita molesta , G. funebrana , and Hedya nubiferana (Lep., Tortricidae): ( E )- and ( Z )- 46 , 51 Plutella xylostella (Lep., Plutellidae): 47 , 52 moth (Lep.) 48–52 , 47 Keiferia lycopersicella (Lep., Gelechiidae): 53 , 53 Anthistarcha binocularis (Lep., Gelechiidae): 54 and 55 , 54 Illiberis pruni (Lep., Zygaenidae): 56 and 57 , 55 Rhyacionia buoliana (Lep., Tortricidae): 58 , 50 Phyllonorycter blancardella (Lep., Gracillariidae): ( Z )- 59 , 56 Ostrinia furnacalis (Lep., Crambidae): ( E )- and ( Z )- 60 , 57 Melanotus communis (Col., Elateridae): 61 , 58 Dasineura pyri (Dip., Cecidomyiidae): 62 , 59 Ithomia salapia (Lep., Nymphalidae): 63 and 64 , 60 Cydia pomonella (Lep., Tortricidae): 65 , 61,62 Stathmopoda masinissa (Lep., Stathmopodidae): 66 and 67 , 63 Lobesia botrana (Lep., Tortricidae): 68 , 64–66 Malacosoma neustria and Dendrolimus punctatus (Lep., Lasiocampidae): 69 , Spodoptera littoralis and S. litura (Lep., Noctuidae): 70 , 67 Thaumetopoea bonjeani (Lep., Notodontidae): 71 and 72 , 68 Acanthoscelides obtectus (Col., Chrysomelidae): 73 , 69 Plodia interpunctella hb. (Lep., Pyralidae): 74 , 70 Pectinophora gossypiella (Lep., Gelechiidae): 75 , 29,71 Spodoptera exigua (Lep., Noctuidae): 76 , 72 Phyllonorycter ringoniella (Lep., Gracillariidae): 77 , 73,74 Loepa sakaei (Lep., Saturniinae): 78 , 75 Symmetrischema tangolias (Lep., Gelechiidae): 79 , 76 Tuta absoluta (Lep., Gelechiidae):…”