Submitted to: Tetrahedron
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 2/11/2005
Publication Date: 5/10/2005
Citation: Khrimian, A. 2005. The geometric isomers of methyl-2,4,6-decatrienoate, including pheromones of at least two species of stink bugs.. Tetrahedron 61(15): 3651-3657. Interpretive Summary: The brown marmorated stink bug (BMSB) has recently been introduced to the U.S. from Asia and established in the Northeast thus posing a potential threat to many commercial crops, e.g., peach, apple, soybean, grapes, raspberries, and ornamental plants. Literature data and our preliminary studies indicated that BMSB is cross-attracted to pheromones of two other stink bugs, brown-winged green bug, which does not occur in the U.S., and red-shouldered stink bug, which is native to the U.S. This paper reports synthesis of eight chemical components of these pheromones. The availability of an attractant for monitoring the spread of BMSB in the U.S. would be invaluable to extension and pest management programs. The synthetic methods described may be of interest to pheromone chemists.
Technical Abstract: All eight geometric isomers of methyl 2,4,6-decatrienoate were synthesized from readily accessible starting materials by fully exploiting Wittig-type olefinations, and taking advantage of an easy separation of 2E and 2Z unsaturated esters. The aggregation pheromone of the brown-winged green bug, Plautia stali, methyl (E,E,Z)- 2,4,6-decatrienoate (also a cross-attractant for the brown marmorated stink bug, Halyomorpha halys), was expediently produced in two easy steps from (E)-4,4-dimethoxy-2-butenal in 55% yield. The sex pheromone of the red-shouldered stink bug, Thyanta pallidovirens, methyl (E,Z,Z)- 2,4,6-decatrienoate, was conveniently synthesized from 2,4-octadiyn-1-ol in 32% yield using in situ manganese dioxide oxidation-Wittig condensation in a key step.