Scalable synthesis of methyl (E,E,Z)-2,4,6-decatrienoate, the aggregation pheromone component of the brown-winged green bug, Plautia stali

Abstract

Methyl (E,E,Z)-2,4,6-decatrienoate (1) is the aggregation pheromone of the brown-winged green bug, Plautia stali and is also a pheromone synergist of the brown marmorated stink bug, Halyomorpha halys pheromone. A scalable and controllable synthesis of methyl (E,E,Z)-2,4,6-decatrienoate (1) was achieved in 5 steps. The stereoselective formation of the 4E, 6Z conjugated double bond was accomplished by a tandem addition reaction of acrolein with acetylene and the 2E double bond was formed by a Heck reaction. The pheromone was obtained in 99 % stereochemical purity and 40 % overall yield starting from (Z,E)-7-bromo-4,6-heptadienal.