A New Synthesis of the Sex Pheromone of the Indian Meal Moth Plodia Interpunctella hb. (Lepidoptera, Pyralidae)

Abstract

New synthesis of (9Z,12E)-9,12-tetradecadien-1-yl acetate, the sex pheromone of the indian meal moth Plodia interpunctella (Lepidoptera, Pyralidae), were developed. The synthesis was based on a C8+C2=C10 and C10+C4=C14 coupling scheme. The route involves, as the key step, the use of the mercury derivative of the terminal-alkyne -functionalised as intermediate.The first coupling reaction took place between 1-tert-butoxy-8-bromo-octane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-dec-9-yne, which is transformed in di[tert-butoxy-dec-9-yne]mercury.In the second coupling reaction, the mercury derivative was directly lithiated and then alkylated with (E)-1-bromo-2-butene obtaining 1-tert-butoxy-(9-yne,12E)-9,12-tetradecaenyne. After stereoselective reduction in the presence of NiP-2 catalyst and acetylation gave (9Z,12E)-9,12-tetradecadien-1-yl acetate with 82% isomeric purity.

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

“…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): 80 and 81 , 50,77,78 Conopomorpha cramerella (Lep., Gracillariidae) 82 and 83 , 79 Ectropis obliqua (Lep., Geometridae): 84 , 27 Cylas formicarius (Col., Brentidae): 85 , 48 Acanthoscelides obtectus (Col., Chrysomelidae): 86 and 87 , 80,81 Cactoblastis cactorum (L...…”

“…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][65][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. 85 Two pheromone esters with conjugated E,Z-congured double bonds, (5E,7Z)-dodeca-5,7-dienyl acetate (69) and (9Z,11E)-dodeca-9,11-dienyl acetate (70), were synthesized via a cross-metathesis reaction by Luo et al (Scheme 4). 67 The Zselective cross-metathesis of (3E)-1,3-dienes and terminal alkenes mediated by ruthenium-benzylidene Grubbs catalyst A afforded the target E,Z-pheromones 69 and 70 in a single convergent step with 30 and 56% yields, respectively.…”