Synthesis of the sex pheromone of the Japanese beetle

Abstract

Abstract--The stereospecific synthesis of the sex pheromone produced by the female Japanese beetle (Popilliajaponica Newman), (Re Z)-5-1-decenyl)-dihydro-2(3H)-furanone, is described. The pure synthetic R,Z form is a powerful attractant for males of the species in field bioassay8 and was competitive in attractiveness with live females, whereas the racemic Z isomer and the S,Z enantiomer were strong inhibitors of male response. The saturated analogs of both enantiomers were also synthesized stereospecifically.

Asymmetric synthesis of (R,Z)-(-)-5-(1-decenyl)oxacyclopentan-2-one, the pheromone of the Japanese beetle.

“…involved (R)-(-)-glutamic acid as the starting material. 2) Since then a number of syntheses have been reported.3~8) Our earlier synthesis depended on the optical resolution of an taminated with a varying amount of (R)-7 generated by transesterification. The optical purity of (i?…”

Chiral Synthesis of (R)-(-)(5Z)-4-Hydroxy-5-tetradecenoic Acid-4-lactone

“…In spite of the low yield experienced in the deoxygenation reac tion of 8, conditions were established for the mild hydrolysis of 10, using 0.01 N hydrochloric acid in TH F:H 20 , 1:1 at 5 5 -6 0 °C, which gave 11 in good yield. The target lactone ( -) -l was obtained by Collins [43] oxidation of 11 and was characterized by elemental analysis and spectral data which were in good agreem ent with those published for (R )-(-)-(5Z)-4-hydroxy-5-tetradecenoic acid-ylactone [14,16,19,45]. The carbohydrate chiral tem plate approach, as outlined in this research, as com pared to the methods described before, does not appear to be a viable route to chiral-lactones.…”

“…DM SO (50 ml) was introduced via syringe under a stream of argon and the mixture was heated at 7 5 -8 0 °C for 45 min. The resulting solution of methylsulfinyl carbanion [45] was cooled in an ice-water bath and nonyltriphenylphosphonium bromide [43] (24.2 g, 0.052 mol) in warm DMSO (50 ml) was added. The resulting dark red solution of the ylide was stirred at room tem perature for 20 min before use.…”

Japanese Beetle and Other Coleoptera Feeding on Grapevines in Eastern North America

“…Male extract caused greater electroantennogram response than did a female extract (Adler and Jacobson 1971 ) . The sex pheromone was eventually described as ( R,Z )-5-1-decenyl)-dihydro-2(3 H )-furanone (Doolittle et al 1980 ) and given the name Japonilure. The R enantiomer is required for attraction and contamination with small amounts of the S enantiomer inhibits attraction.…”