Study On The Total Synthesis And Biological Activity Of Two Insect Sex Pheromones With Chiral Methyl Side Chains

Due to the resistance,toxicity,and residue problems of traditional pesticides,pesticide scientists propose that the future direction of pesticide research should be environmentally friendly“green pesticides”,and insect pheromones belong to this category.Based on the concept of"green pesticides",this article used chiral additives R-,S-BOZ and chiral ligand R-Me-CBS to induce chiral methyl groups,and two insect sex pheromones with chiral methyl side chains were synthesized:Psacothea hilaris,Pine sawflies.On this basis,the ELISA was used to analyze the level of sex pheromone content of the Psacothea hilaris in（R,Z）-21-methyl-8-tripentadecene and（R,Z）-21-methyl-8-tritetradecene,（2S,3S,7S）-3,7-dimethylpentadecan-2-ol acetate and propionate and（2R/S,3S,7S）-3,7-Dimethylpentadecan-2-ol acetate and propionate were tested for the biological activity of the emergence adults of Pine sawflies.The main research contents and results of this paper are as follows:1.Explored the sex pheromone（R,Z）-21-methyl-8-tripentadecene and the total synthesis of its derivative,namely（R,Z）-21-methyl-8-tritetradecene.Constructed chiral C5 fragment（R）-4-（benzyloxy）-2-methylbutan-1-ol with cheap R-BOZ,and then adopted the construction strategy of"C12（or C11）+C5+C11+C8"carbon skeleton,coupling the C-C backbone through the Wittig reaction,and finally completed the total synthesis of the Psacothea hilaris sex pheromone and its derivatives in 10 linear steps,with the total yields of 36.2%and 36.0%.A total of 24 intermediates were synthesized,and 14 reported structures were not seen;2.Explored the asymmetric total synthesis of Pine sawflies sex pheromone（2S,3S,7S）-3,7-dimethylpentadecan-2-ol acetate and propionate.Using decanoyl chloride andγ-butyrolactone as starting materials,chiral methylation was induced by S-BOZ to obtain chiral C11 fragment（S）-2-methyldec-1-ol and C5 fragment（S）-3-Methyl-4-（（triisopropylsilyl）oxy）butan-1-ol.Wittig reaction was used to connect the two chiral fragments,after hydrogenation reduction,DMP oxidation,Me Li addition,and R-Me-CBS catalytic reduction,（2S,3S,7S）-3,7-dimethylpentadecan-2-ol was obtained,and finally acylated with acetyl chloride and propionyl chloride to synthesize pine leaf peak sex pheromone（2S,3S,7S）-3,7-dimethylpentadecan-2-ol acetate and propionate.The target products（2S,3S,7S）-3,7-dimethylpentadecan-2-ol acetate and propionate were synthesized with a total yield of 42.0%through 12 linear reactions,and intermediates were synthesized together.A total of 17intermediates were synthesized,of which 7 new structures have not been reported;3.The 41 compounds synthesized in this article were characterized by ¹H-NMR,¹³C-NMR,HRMS（ESI）,and the optical rotation values of the compounds with optical activity were determined;4.ELISA was used to test the levels of sex pheromone of Psacothea hilaris in the（R,Z）-21-methyl-8-tripentadecene and its derivatives（R,Z）-21-methyl-8-tritetradecene,and the results were 87.71%and 81.36%,respectively.The effects of（2S,3S,7S）-3,7-dimethylpentadecan-2-ol acetate and（2R/S,3S,7S）-3,7-dimethylpentadecanoate in attracting the adults of Pine sawflies emergence were compared through forest experiments.