Substrate specificity of the epoxidation reaction in sex pheromone biosynthesis of the Japanese giant looper (Lepidoptera: Geometridae)

Transport of a hydrophobic biosynthetic precursor by lipophorin in the hemolymph of a geometrid female moth which secretes an epoxyalkenyl sex pheromone

“…The syntheses of 19,19,19-trideuterated (Z,Z,Z)-3,6,9-nonadecatriene (D 3 -Z3,Z6,Z9-19:H, 498% purity) and unlabeled (Z,Z,Z)-3,6,9-tricosatriene (Z3,Z6,Z9-23:H, 498% purity) have been previously reported (Miyamoto et al, 1999;Ando et al, 1993). By the similar route to that for D 3 -Z3,Z6, Z9-19:H, 19,19,19- …”

“…While our knowledge is still limited regarding the biosynthesis of Type II pheromones, it has been demonstrated that it is quite different from that of Type I pheromones. The type II pheromones are not produced de novo but are presumably derived from linolenic and linolic acids coming from plants (Rule and Roelofs, 1989), and the enzymatic process in a pheromone gland is only epoxidation (Miyamoto et al, 1999). Polyunsaturated hydrocarbons, which are precursors of epoxy pheromones and sometime pheromone components themselves, are expected to be produced outside the pheromone gland, probably in oenocytes or a fat body, and transported to the gland via the hemolymph (Howard and Blomquist, 2005;Jurenka, 2005;Wei et al, 2003).…”

“…This epoxy pheromone is formed from the corresponding polyunsaturated hydrocarbon, (Z,Z,Z)-3,6,9-nonadecatriene (Z3,Z6,Z9-19:H), in a pheromone gland (Miyamoto et al, 1999). Z3,Z6,Z9-19:H was detected in the hemolymph of the females, and the deuterated triene injected into the abdomen of the females was also converted to the epoxy pheromone after incorporation into the pheromone glands (Wei et al, 2003).…”

Chiral HPLC resolution of monoepoxides derived from 6,9-dienes and its application to stereochemistry assignment of fruit-piercing noctuid pheromone

“…In a field trial, the racemic mixture of 2e played the role as a main pheromone component more effectively than the (9S,10R)-isomer. The stereochemistry of the minor component (3e) is still unknown, but the same 9S,10R configuration is expected if one monooxygenase catalyzes the epoxidation of both dienyl and trienyl precursors as the epoxidation enzyme of A. s. cretacea (Miyamoto et al, 1999). EAG responses to both enantiomers of 3e agree with this speculation.…”

Epoxyalkenyl sex pheromones produced by female moths in highly evolved groups: biosynthesis and its endocrine regulation

“…These in vivo experiments revealed that the epoxidase regiospecifically attacked the (Z)-3-double bond of straight chain hydrocarbons regardless of their length and unsaturated degree. 12) The low substrate specificity indicated that the production of a species-specific pheromone might be caused essentially by strict production of an unsaturated hydrocarbon. In vivo experiments with another geometrid species, Hemerophila atrilineata, secreting cis-9,10-exoxy-(Z,Z)-3,6-octadecadiene (Z3,Z6,epo9-18:H), also clarified the epoxidation step, 13) however, characterization of the epoxygenase has not been accomplished, and the pathway of triene biosynthesis has not been confirmed.…”