The geometric isomers of methyl-2,4,6-decatrienoate, including pheromones of at least two species of stink bugs

Khrimian, Ashot

doi:10.1016/j.tet.2005.02.032

Cited by 30 publications

(34 citation statements)

References 27 publications

(23 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Despite notable and promising recent efforts (44), all eight possible stereoisomers of conjugated 2,4,6-trienoic esters do not appear to have been prepared in good yields (≥70-80%) and ≥95% selectivity. Accordingly, we decided to accomplish these goals through applications of the knowledge and experience gained in the preceding sections.…”

Section: Resultsmentioning

confidence: 98%

Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Wang

Mohan

Negishi

2011

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

All four stereoisomers (7-10) of ethyl undeca-2,4-dienoate were prepared in ≥98% isomeric purity by Pd-catalyzed alkenylation (Negishi coupling) using ethyl (E)-and (Z)-β-bromoacrylates. Although the stereoisomeric purity of the 2Z,4E-isomer (8) prepared by Suzuki coupling using conventional alkoxide and carbonate bases was ≤95%, as reported earlier, the use of CsF or n Bu4NF as a promoter base has now been found to give all of 7-10 in ≥98% selectivity. Other widely known methods reveal considerable limitations. Heck alkenylation was satisfactory for the syntheses of the 2E,4E and 2E,4Z isomers of ≥98% purity, but the purity of the 2Z,4E isomer was ≤95%. Mutually complementary HornerWadsworth-Emmons and Still-Gennari (SG) olefinations are also of considerably limited scopes. Neither 2E,4Z nor 2Z,4Z isomer is readily prepared in ≥90% selectivity. In addition to (2Z,4E)-dienoic esters, some (2Z,4E,6E)-and (2Z,4E,6Z)-trienoic esters have been prepared in ≥98% selectivity by a newly devised Pd-catalyzed alkenylation-SG olefination tandem process. As models for conjugated higher oligoenoic esters, all eight stereoisomers for ethyl trideca-2,4,6-trienoate (23-30) have been prepared in ≥98% overall selectivity.highly selective synthesis | Pd-catalyzed Negishi coupling A lkenes represent a large number of natural products of bioactive and medicinally important compounds. Of interest in this study are those containing conjugated dienes and oligoenes (1-11) (Fig. 1). Among numerous known methods for the syntheses of alkenes including conjugated dienes and oligoenes (12, 13), carbonyl olefination reactions, notably Wittig olefination (14) and its variants, such as Horner-Wadsworth-Emmons (HWE hereafter) (15, 16), and Still-Gennari (SG hereafter) (17) as well as Ando (18) modifications have been widely used along with related Si-promoted (Peterson) (19) and S-promoted (Julia and Paris) (20) olefination reactions. As useful as these reactions are, they often lack very high (≥98%) stereoselectivity.In search for highly (≥98%) stereoselective alkene synthesis methodology, our attention was initially drawn to alkyne hydroboration, which generally proceeds in >99% syn-selectivity. Following some promising leads of Brown (21) and Zweifel and co-workers (22-25), we reported in 1973 a couple of highly selective routes to 1,4-disubstituted (E,E)-and (E,Z)-1,3-dienes (1, 3, 26), which appear to represent the earliest syntheses of unsymmetrically substituted conjugated dienes in very high (≥97%) selectivity via organometallic alkenylation.Despite highly selective and satisfactory results described above, our continued search for a more generally applicable and straightforward route to conjugated di-and oligoenes led to the discovery in 1976 of the Pd-catalyzed alkenyl-alkenyl coupling with alkenylalanes (27) and subsequently with alkenyl derivatives containing Zr (28) and Zn (29), collectively known as Negishi coupling (30,31). Along with the subsequently developed alkenylboron version (Suzuki coupling) (32-34), the Pd-catalyzed alken...

show abstract

Section: Resultsmentioning

confidence: 98%

Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Wang

Mohan

Negishi

2011

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

show abstract

“…The aggregation compound methyl (E,E,Z)-2,4,6-decatrienoate used in this study was synthesized by USDA-ARS in Beltsville, MD following the procedures outlined by Khrimian (2005). Rubber septa were impregnated with 2.5 mg of methyl (E,E,Z)-2,4,6-decatrienoate.…”

Section: Methodsmentioning

confidence: 99%

“…Traps baited with methyl (E,E,Z)-2,4,6-decatrienoate, the aggregation pheromone of a sympatric Asian species, Plautia stali Scott (Hemiptera: Pentatomidae), are highly attractive to H. halys (Khrimian 2005). This pheromone has been used in its native and nonnative habitat for monitoring populations of H. halys (Lee et al 2002, Adachi et al 2007, Khrimian et al 2008; however, no studies evaluating traps for H. halys have been done in soybean in either Asia or the United States.…”

mentioning

confidence: 99%

Seasonal Phenology and Monitoring of the Non-Native <I>Halyomorpha halys</I> (Hemiptera: Pentatomidae) in Soybean

2011

View full text Add to dashboard Cite

“…4493-42-9), was purchased from Degussa Fine Chemicals (Marl, Germany) and stored at Ϫ20ЊC until used. Methyl (E,E,Z)-2,4,6-decatrienoate was synthesized as previously described (Khrimian 2005), as were the trans-and cis-(Z)-␣-bisabolene epoxides (Chen et al 2000).…”

Section: Methodsmentioning

confidence: 99%

Pheromone Attraction and Cross-Attraction ofNezara,Acrosternum, andEuschistusspp. Stink Bugs (Heteroptera: Pentatomidae) in the Field

et al. 2010

View full text Add to dashboard Cite

Detecting infestations of stink bugs (Heteroptera: Pentatomidae) using pheromones remains problematic, particularly so in the United States for the exotic stink bug, Nezara viridula L., and our native stink bug, Acrosternum hilare (Say). Therefore, we conducted a 2-yr on-farm study to examine the attractiveness and possible cross-attraction of the reported pheromones for N. viridula and A. hilare and those previously discovered for Euschistus servus (Say) and Plautia stali Scott to N. viridula, A. hilare, and E. servus. The attractiveness of selected pentatomid pheromones to tachinid parasitoids of stink bugs was also examined. We showed for the first time under field conditions that N. viridula can be trapped with its reported pheromone, a 3:1 trans- to cis-(Z)-alpha-bisabolene epoxide blend. In fact, attraction of N. viridula increased with higher pheromone doses. Traps baited with a 5:95 trans- to cis-(Z)-alpha-bisabolene epoxide blend, the reported male-produced A. hilare attractant pheromone, failed to attract significantly more A. hilare than did unbaited control traps. Instead A. hilare was significantly cross-attracted to the P. stali pheromone [methyl (E,E,Z)-2,4,6-decatrienoate]. The E. servus pheromone [methyl (E,Z)-2,4-decadienoate], either alone or in combination with P. stali pheromone, was more attractive to E. servus than to N. viridula, P. stali, or A. hilare pheromones. In general, tachinid parasitoids were found responsive to the male-specific volatiles of their known hosts, including the attractiveness of Trichopoda pennipes (F.) to sesquiterpenoid blends characteristic of A. hilare and N. viridula. A tachinid parasitoid of E. servus, Cylindromyia sp., seemed to be attracted to E. servus pheromone. In conclusion, our results indicate that stink bug traps baited with lures containing N. viridula pheromone blend, P. stali pheromone, and E. servus pheromone have the greatest potential for detecting populations of N. viridula, A. hilare, and E. servus, respectively, in diversified agricultural landscapes.

show abstract

The geometric isomers of methyl-2,4,6-decatrienoate, including pheromones of at least two species of stink bugs

Cited by 30 publications

References 27 publications

Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Seasonal Phenology and Monitoring of the Non-Native <I>Halyomorpha halys</I> (Hemiptera: Pentatomidae) in Soybean

Pheromone Attraction and Cross-Attraction ofNezara,Acrosternum, andEuschistusspp. Stink Bugs (Heteroptera: Pentatomidae) in the Field

Contact Info

Product

Resources

About