Invasive Stink Bugs and Related Species (Pentatomoidea)

690 Invasive Stink Bugs and Related Species (Pentatomoidea)

The identifications of aggregation pheromone components of H. halys and M. histrionica were
accomplished by careful matching of GC retention times of components in aeration extracts of male
bugs with standards of known relative and absolute stereochemistries from the stereoisomeric library
of 10,11-epoxy-1-bisabolen-3-ols, on two enantioselective columns (Chiraldex G-TA and Hydrodex
β-6TBDM; Khrimian et al. 2014a,b).
In field bioassays, both the major ( 37 ) and the minor ( 38 ) pheromone components attracted adult
H. halys of both sexes. Epoxide 37 was more attractive than the minor component 38 , whereas the mixture
at the natural 3.5:1 ratio was more attractive than either component alone. The mixture and  the major

a

H HH

O

HO

HO

HO

O OH

OH

OH

H H

H

O OH OH

H H

OH

OHHO O

H H H

HO HO

HO O

OH

HHH

HO

HO O

OH

HH

HO

(^3940) , 24% yield, 96:4 dr 41 , 5% yield, 86:14 dr
H. halys and M. histrionica
aggregation pheromones
main component
H. halys aggregation pheromone
minor component
O. poecilus
sex pheromone
M. histrionica
aggregation
pheromone
minor component
37 , 60%, 95:5 dr
44 , 66%, 95:5 dr
45 , 30% yield, 91:9 dr 46 , 5% yield, 89:11 dr
40
42
40
39
47
48
38 , 51%, 95:5 dr
49 , 3% yield, 93:7 dr 50 , 26% yield, 96:4 dr
43
b c
75%
d c
e
c
e+
91%

• b
  70%


• 
  

  FIGURE 15.7 Syntheses of individual stereoisomers of 1,10-bisaboladien-3-ols and 10,11-epoxy-1-bisabolen-3-ols.
  a) Me 3 A l /[R h(cod)Cl] 2 /(R)-BINAP/SiO 2 separation; b) AD-mix-b; c) 1. MsCl/Py, 2. KOH/MeOH; d) AD-mix-a; e) Me 3 Al/
  [R h(cod)Cl] 2 /(S)-BINAP/SiO 2 separation.