Expedient synthesis of bisabolenol stink bug pheromones via stereodefined cyclohex-2-enones

TETRAHEDRON LETTERS

卷:58

Article

Shirali, Shyam¹  Guzman, Filadelfo¹  Weber, Donald C.¹  Khrimian, Ashot¹ 

[1] USDA ARS, Invas Insect Biocontrol & Behav Lab, Beltsville Agr Res Ctr, Bldg 007,10300 Baltimore Ave, Beltsville, MD 20705 USA

关键词: Rice stink bug;    Oebalus poecilus;    Brown marmorated stink bug;    Halyomorpha halys;    Harlequin bug;    Murgantia histrionica;    Pheromones;    Michael addition;    Robinson annulation;   

DOI  :  10.1016/j.tetlet.2017.04.050

来源: Elsevier

【 摘 要 】

We recently synthesized all stereoisomers of 1,10-bisaboladien-3-ol and 10,11-epoxy-1-bisabolen-3-ol, including three stink bug pheromones, via a rhodium-catalyzed asymmetric addition of trimethylaluminum to diastereomeric mixtures of cyclohex-2-enones. However, yields of trans isomers were low, and scaling reactions using expensive catalysts were cumbersome. Now we describe a new synthesis of bisabolenol stink bug pheromones via (S)- and (R)-4-((R)-6-methylhept-5-en-2-yl)cyclohex-2-enones prepared by enantioselective Michael additions of methyl vinyl ketone to (S)- and (R)-citronellals and lithium hydroxide monohydrate-catalyzed stereoselective cyclizations of intermediate ketoaldehydes. Addition of methyllithium to these enones provided cis- and trans-1,10-bisaboladien-3-ols, which were separated by chromatography on silica and further converted to 10,11-epoxy-l-bisabolen-3-ols. Thus, we developed more convenient syntheses of pheromones of the rice stink bug, the harlequin bug, and brown marmorated stink bug. Published by Elsevier Ltd.

【 授权许可】

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