Synthesis of the four stereoisomers of 7-acetoxy-15-methylnonacosane, a component of the female sex pheromone of the screwworm fly, Cochliomyia hominivorax

The four stereoisomers of 7-acetoxy-15-methylnonacosane (1), a component of the female sex pheromone of the New World screwworm fly (Cochliomyia hominivorax) were synthesized. The stereogenic center at C-15 of 1 originated from that of the enantiomers of citronellal, and that at C-7 was generated by lipase-catalyzed asymmetric acetylation of (3RS,11R)- and (3RS,11S)-17-methyl-1-trimethylsilylpentacos-1-yn-3-ol (13). Three of the stereoisomers of 1 showed equivalent good pheromone activity, while the activity of (7R,15R)-1 was weak.     

Activity of the diastereoisomers of 13,23-dimethylpenta-triacontane, the sex pheromone of Glossina pallidipes, and comparison with the natural pheromone

ABSTRACT. All three synthetic diastereoisomers of 13,23-dimethyl-pentatriacontane, the pheromone of Glossina pallidipes (Austen), have been tested in the G. pallidipes sex pheromone bioassay, together with one of the four diastereoisomers of 13,17-dimethylpentatriacontane, originally proposed as a candidate pheromone of G. pallidipes. Of the three isomers of 13,23-dimethylpentatriacontane only the (13R,23S) isomer was active with an ED-50 of 4.47±1.09/μg (mean±SD). The (13R,17R)-13,17-dimethylpentatriacontane was inactive. The diastereo-isomeric mixtures of 13,17- and 13,23-dimethylpentatriacontane were active with ED-50 values of 17.88±1.25/μg and 8.88±1.15μg respectively. The natural pheromone was active with an ED-50 of 8.07±1.17 μg indicating it to be a diastereoisomeric mixture.     

Determination by HPLC fluorescence analysis of the natural enantiomers of sex pheromones in the New World screwworm fly, Cochliomyia hominivorax

Abstract.  Bioassays of six racemic synthesized candidate sex pheromone compounds against male New World screwworm Cochliomyia hominivorax (Coquerel) flies showed that the most potent bioactivity was found with 6-acetoxy-19-methylnonacosane and 7-acetoxy-15-methylnonacosane compared with four other isomeric acetoxy nonacosanes and a larger aliphatic ketone. As all these methyl-branched compounds have two asymmetric carbons and four possible enantiomers, characterization of the natural enantiomers was essential. All four enantiomers for the two most bioactive isomers of the natural sex pheromone were synthesized for bioassay. Hydrolysis and derivatization of these enantiomers with different fluorescent reagents was followed by column-switched high-performance liquid chromatography. The use of two linked, reversed-phase columns of different polarity held at sub-ambient temperatures allowed good separation of each enantiomer. This analysis applied to natural material was successful, as (6 R ,19 R )-6-acetoxy-19-methylnonanocosane, and (7 R ,15 R )- and (7 R ,15 S )-7-acetoxy-15-methylnonanocosane were detected in extracts of recently colonized female flies.     

1,3,5,7-Tetramethyldecyl Formate,Lardolure: Aggregation Pheromone of the Acarid Mite,Lardoglyphus konoi (Sasa et Asanuma) (Acarina: Acaridae)

From an acarid mite, Lardoglyphus konoi (Sasa et Asanuma) (Acarina: Acaridae), with its culture medium, an aggregation pheromone was isolated. The structure of the pheromone was determined as 1,3,5,7-tetramethyldecyl formate and identified by 11 steps of organic synthesis. The absolute configuration of C₁ was assigned as R. The compound has been assigned the trivial name lardolure. The synthesized diastereomeric mixture of racemates showed one-tenth of the activity of the natural pheromone against the test mite, Carpoglyphus lactis.     

Synthesis of (3E, 5Z)-3,5-dodecadienylacetate, the sex pheromone of Phtheochroa cranaodes (Lepidoptera: Tortricidae

(3E, 5Z)-3,5-Dodecadienyl acetate, the female sex pheromone of Phtheochroa cranaodes, was regio and stereo-selectively synthesized from 1-octyne and (E)-4bromo-3-buten-1-ol by using Pd(PPh3)4, CuI and piperidine to afford the enyne (5). Further elaboration afforded the target pheromone. The synthetic pheromone was identified with the natural product by its MS and IR, data GLC retention time and biological activity.     

Determination of the absolute configuration of quercivorol, (1S,4R)-p-menth-2-en-1-ol, an aggregation pheromone of the ambrosia beetle Platypus quercivorus (Coleoptera: Platypodidae)

A pair of enantiomers of trans-p-menth-2-en-1-ol, an aggregation pheromone of Platypus quercivorus, was synthesized from (S)- and (R)-limonene. The retention time of the aggregation pheromone from the insect coincided with that of (1S,4R)-p-menth-2-en-1-ol synthesized from (S)-limonene from GC analyses with a chiral column, enabling the absolute configuration of the aggregation pheromone to be determined as (1S,4R).     

Enzymatic Reduction of Sorbic Acid to trans-4-Hexmol

The sex pheromone of the citrus mealybug (Pseudococcus cryptus), [(1R,3R)-3-isopropenyl-2,2-dimethylcyclobutyl]methyl 3-methyl-3-butenoate, was synthesized from (+)-α-pinene in five operational steps in a 43% overall yield. The synthetic pheromone was identical with the natural pheromone in ¹H-NMR and mass spectroscopic properties, and showed almost the same pheromonal activity as the natural pheromone.     

Refrigerated eggs of Riptortus pedestris (Hemiptera: Alydidae) added to aggregation pheromone traps increase field parasitism in soybean

Riptortus pedestris (F.) (Hemiptera: Alydidae) is a key pest of soybean [Glycine max (L.) Merr.] in Korea and Japan. Aggregation pheromone traps have been used to attract R. pedestris. An aggregation pheromone, produced by males of R. pedestris, also attracts the egg parasitoid, Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae). As a new method of pest management, we propose the use of nonviable host eggs in the pheromone trap together to both trap R. pedestris and propagate parasitoids on host eggs attached to the trap. Approximately ten-thousand nonviable refrigerated host eggs were placed outside pheromone traps in three soybean fields (0.167-0.284 ha.). During the sampling period from 7 August to 8 October in 2008, statistical significance of treatment was not found in any life stage of R. pedestris population. However, significantly higher parasitism of both natural (78-91%) and refrigerated eggs (36-59%) occurred in the treatment sites, compared with control sites where parasitism was 0-62% and 16-34% on natural and refrigerated eggs, respectively. The proportion of bean pods with stink bug feeding damage was significantly reduced by 47% in the treatment sites. This study is the first trial of an integrated pest management (IPM) strategy using both nonviable host eggs and trap that simultaneously targets both the pest and its natural enemy.     

Perception of volatiles associated with sex and food by different adult forms of the black bean aphid, Aphis fabae

Abstract. Electroantennograms (EAGs) were recorded from adult male and asexual forms (winged and wingless virginoparae and gynoparae) of the black bean aphid, Aphis fabae , during stimulation with two sex pheromone components, (+)-(4a S ,7 S ,7a R )-nepetalactone and (-)-(1 R ,4a S ,7 S ,7a R )-nepetalactol, as well as six plant volatiles, i.e. ( E )-2-hexenal, ( E )-2-hexenol-1, ( Z )-3-hexenol-1, ( Z )-3-hexenyl acetate, hexanal and allyl isothiocyanate. The male antennae are 1000-10,000 times more sensitive to nepetalactol and nepetalactone than to the plant compound ( E )-2-hexenal. Besides this marked difference of EAG peak responses in males, the EAG rise and decay are slower for the sex pheromone components. Males are also much more sensitive to the sex pheromone components than asexual females. This high sensitivity correlates with a predominance of antennal secondary rhinaria, the major sites of pheromone perception in the male. However, it is the primary rhinaria on the antennae of the wingless asexual females that are responsible for pheromone perception. Male antennae are as responsive as the asexual female antennae to the plant volatiles. The specialization of the male for mate location is discussed.     

Synthesis of (R,Z)-7, 15-Hexadecadien-4-olide,the Sex Pheromone of the Yellowish Elongate Chafer (Heptophylla picea)

(R, Z)-7,15-Hexadecadien-4-olide, the sex pheromone of the yellowish elongate chafer (Heptophylla picea), was synthesized from l-malic acid in 15 steps. The synthetic pheromone was identical with the natural product in its MS, IR, GLC retention time, and biological activity.     

Conserved repertoire of orthologous vomeronasal type 1 receptor genes in ruminant species

Background  

In mammals, pheromones play an important role in social and innate reproductive behavior within species. In rodents, vomeronasal receptor type 1 (V1R), which is specifically expressed in the vomeronasal organ, is thought to detect pheromones. The V1R gene repertoire differs dramatically between mammalian species, and the presence of species-specific V1R subfamilies in mouse and rat suggests that V1R plays a profound role in species-specific recognition of pheromones. In ruminants, however, the molecular mechanism(s) for pheromone perception is not well understood. Interestingly, goat male pheromone, which can induce out-of-season ovulation in anestrous females, causes the same pheromone response in sheep, and vice versa, suggesting that there may be mechanisms for detecting "inter-species" pheromones among ruminant species.     

Acid labile ComX pheromone from Bacillus mojavensis RO-H-1

Bacillus mojavensis strain RO-H-1 produces a posttranslationally modified hexapeptide, the ComX(RO-H-1) pheromone, that stimulates natural genetic competence controlled by quorum sensing. LC/ESI-MS analysis of partially purification of the ComX(RO-H-1) pheromone suggested a precise modification in its tryptophan residue. The corresponding ComX(RO-H-1) pheromone prepared by solid-phase synthesis was identical to the natural pheromone, and showed significant biological activity. These results indicated that the posttranslational modification of the ComX(RO-H-1) pheromone was geranylation on the tryptophan residue, resulting in the formation of a tricyclic structure. The ComX(RO-H-1) pheromone was immediately dehydrated by acid because of its extreme acid lability.     

合成黑翅土白蚁踪迹信息素类似物的生物活性

合成了黑翅土白蚁踪迹信息素类似物(Z,Z)-3,6-十二碳二烯醇-1（DDE-OH）,该类似物对黑翅土白蚁工蚁具有和信息素提取物类似的行为反应。活性反应阈值为10^-3～10 ng/cm,大于10 ng/cm时产生较强的驱避作用。最佳活性浓度DDE-OH与信息素提取物的活性反应之间没有显著差别。     

New synthesis of the (3Z,6Z,9S,10R)-isomers of 9,10-epoxy-3,6-henicosadiene and 9,10-epoxy-1,3,6-henicosatriene, pheromone components of the female fall webworm moth, Hyphantria cunea

(3Z,6Z,9S,10R)-9,10-Epoxy-3,6-henicosadiene (1) and (3Z,6Z,9S,10R)-9,10-epoxy-1,3,6-henicosatriene (5), pheromone components of the female fall webworm moth (Hyphantria cunea Drury), were synthesized by starting from (2S,3R)-2,3-epoxy-4-t-butyldimethylsilyloxy-1-butanol (8). Epoxide 8 was prepared by employing lipase-catalyzed asymmetric acetylation of (+/-)-8 as the key optical resolution step.     

Unisex pheromone detectors and pheromone-binding proteins in scarab beetles

Olfaction was studied in two species of scarab beetle, Anomala octiescostata and Anomala cuprea (Coleoptera: Scarabaeidae: Rutelinae), which are temporarily isolated and use the same sex pheromone compounds, (R)-buibuilactone and (R)-japonilure. Single sensillum recordings in A. octiescostata revealed highly sensitive olfactory receptor neurons (ORNs) (threshold <1 pg) that were tuned to the detection of the green leaf volatile compound (Z)-3-hexenyl acetate. As opposed to similar ORNs in another scarab species, Phyllopertha diversa, in A. octiescostata a diazo analogue elicited much lower neuronal responses than the natural ligand. Detectors for other floral and leaf compounds were also characterized. Extremely stereoselective ORNs tuned to sex pheromone were identified in male and female antennae. Biochemical investigations showed that, in A. octiescostata and A. cuprea, the pheromone-binding proteins (PBPs) isolated from male antennae were identical to PBPs obtained from female antennae. AoctPBP and AcupPBP had seven different amino acid residues. Binding of AoctPBP to (R)-japonilure is shown. PdivOBP1, which is also known to bind to (R)-japonilure, differed from AcupPBP in only two amino acid residues, one at the N-terminus and the other near the C-terminus. The structural features of the Bombyx mori PBP are compared with the sequences of eight known scarab odorant-binding proteins.     

Synthesis of (2S,2'R,3S,4R)-2-(2'-hydroxy-21'-methyidocosanoylamino)-1,3,4-pentadecanetriol,the ceramide sex pheromone of the female hair crab,Erimacrus isenbeckii

The ceramide sex pheromone [(2S,2'R,3S,4R)-2-(2'-hydroxy-21-methyldocosanoylamino)-1,3,4-pentadecanetriol (1)] of the female hair crab (Erimacrus isenbeckii) was synthesized by starting from (S)-serine and 12-bromo-1-dodecanol.     

Metathesis-mediated synthesis of (R)-10-methyl-2-tridecanone, the southern corn rootworm pheromone

(R)-10-Methyl-2-tridecanone, the female sex pheromone of the southern corn rootworm (Diabrotica undecimpunctata howardi Barber), was synthesized in 9 steps from methyl (S)-3-hydroxy-2-methylpropanoate in a 15.7% overall yield. Olefin cross metathesis between (R)-6-methyl-1-nonene and 5-hexen-2-one employing Grubbs' first-generation catalyst was the key step of the synthesis.     

Synthesis of (3E, 5Z)-3,5-Dodecadienylacetate,the Sex Pheromone of Phtheochroa cranaodes (Lepidoptera: Tortricidae)

(3E, 5Z)-3,5-Dodecadienyl acetate, the female sex pheromone of Phtheochroa cranaodes, was regio and stereo-selectively synthesized from 1-octyne and (E)-4-bromo-3-buten-1-ol by using Pd(PPh₃)₄, CuI and piperidine to afford the enyne (5). Further elaboration afforded the target pheromone. The synthetic pheromone was identified with the natural product by its MS and IR, data GLC retention time and biological activity.     

Comparison of efficacy of pheromone dispensing technologies for controlling the grape berry moth (Lepidoptera: Tortricidae) by mating disruption

The efficacy of 3M Sprayable Pheromone for Grape Berry Moth, BASF RAK 1R pheromone dispensers, Isomate GBM pheromone dispensers, and an insecticide program were compared during two seasons for controlling grape berry moth, Endopiza viteana (Clemens), in Niagara peninsula, Ontario, Canada, vineyards. The average number of E. viteana captured in pheromone-baited traps in plots treated with BASF RAK 1R and Isomate GBM dispensers was reduced by 90-100% compared with the average number captured in insecticide-treated plots, indicating a high level of mating disruption. By contrast, there was no difference in the number of moths captured in plots treated with sprayable pheromone and in plots treated with insecticide during the second flight of 1999, suggesting that the sprayable pheromone did not affect the mate-seeking ability of male moths. During the third flight of 1999, and the three flights of 2000, however, the average number of E. viteana captured in plots treated with sprayable pheromone was reduced by 50-99% compared with the average number captured in insecticide-treated blocks, indicating a moderate-to-high level of mating disruption. There was no detectable difference in feeding injury to grape clusters when E. viteana was controlled using two application rates of a sprayable pheromone formulation, two hand-applied pheromone dispensers, or a conventional, insecticide-control program. The disparity between estimated disruption and crop damage in plots treated with sprayable pheromone during the second flight of 1999 suggests that pheromone-baited traps may not provide a reliable estimate of the level of mating disruption when using sprayable pheromone.