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.     

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 (4R,6S,7R)-7-hydroxy-4,6-dimethyl-3-nonanone and (3R,5S,6R)- 6-hydroxy-3,5-dimethyl-2-octanone,the pheromone components of the bostrychid beetle,Dinoderus bifoveolatus

(4R,6S,7R)-7-Hydroxy-4,6-dimethyl-3-nonanone and (3R,5S,6R)-6-hydroxy-3,5-dimethyl-2-octanone, the pheromone components of the bostrychid beetle, Dinoderus bifoveolatus, as well as their (4R,6S,7S)- and (3R,5S,6S)-isomers were synthesized from (2R,4S,5R)- and (2R,4S,5S)-2,4-dimethyl-5-heptanolide, respectively.     

Pheromonal cross-attraction in true bugs (Heteroptera): attraction of Piezodorus hybneri (Pentatomidae) to its pheromone versus the pheromone of Riptortus pedestris (Alydidae)

We investigated the attractiveness of a synthetic form of the pheromone of the soybean stink bug, Piezodorus hybneri (Gmelin), under field conditions, and compared it with that of (E)-2-hexenyl (E)-2-hexenoate, a pheromone component of a competitor, Riptortus pedestris (Fabricius). Many adult stink bugs were attracted to traps baited with 100 mg of the synthetic pheromone (1: 1: one mixture of β-sesquiphellandrene, (R)-15-hexadecanolide, and methyl (Z)-8-hexadecenoate), but few were attracted to 1 or 10 mg. More than twice as many females as males were attracted to this male-produced pheromone. None of the individual pheromone components (30 mg) attracted conspecifics. In summer (June-July), when field P. hybneri were not in diapause, (E)-2-hexenyl (E)-2-hexenoate was more attractive to P. hybneri than the synthetic pheromone. The sex ratio of the adults attracted to the synthetic pheromone was highly female-biased, yet almost equal numbers of both sexes were attracted to (E)-2-hexenyl (E)-2-hexenoate. Most females attracted to both attractants were mated and had mature ovaries. However, adults attracted to (E)-2-hexenyl (E)-2-hexenoate were likely to have less food in their stomach than those attracted to the synthetic pheromone. In late autumn (October-November), when the bugs were in reproductive diapause, both attractants attracted many sexually immature female and male adults that had well-developed fat body. The synthetic pheromone also attracted a large number of conspecific nymphs. These results suggest that P. hybneri pheromone and R. pedestris pheromone component, respectively, have different functions for P. hybneri. The male-produced pheromone system of P. hybneri seems to be sex-related but to have other roles.     

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).     

Sulcatol: population aggregation pheromone in the scolytid beetle, Gnathotrichus sulcatus

The population aggregation pheromone produced by males of Gnathotrichus sulcatus, a timber pest, has been identified from boring dust as a $\text{65}\text{35}$ mixture of the (S)-(+) and the (R)-(?) enantiomers of 6-methyl-5-hepten-2-ol. In field studies beetles were attracted in a 2·65 female: 1 male ratio by racemic synthetic pheromone.     

Identification of sulcatol, a potential pheromone of the ambrosia beetle Gnathotrichus materiarius (Col., Scolytidae)

Abstract: We report the identification of a potential pheromone for Gnathotrichus materiarius (Fitch) (Col., Scolytidae). The population sex ratio is close to 1 : 1, and males initiate attacks on host trees. Headspace and hindgut samples from single males showed the presence of the putative pheromone 6-methyl-5-hepten-2-ol, sulcatol. Unmated males released sulcatol for at least 12 days, and ceased producing the pheromone after 20 days. The peak sulcatol release occurred after 2 days. Males cease production of sulcatol 24 h after being paired with females. Single females were unable to initiate galleries, and no sulcatol was detected from their headspace and hindgut samples. The chiral ratio of the pheromone, observed from headspace samples, was 31% (S)-(+)- and 69% (R)-(−)-sulcatol.     

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.     

Characterization of a putative pheromone biosynthesis-activating neuropeptide (PBAN) receptor from the pheromone gland of Heliothis peltigera

The binding of [(3)H]tyrosyl-PBAN28-33NH(2) to pheromone gland membranes of the moth Heliothis peltigera was investigated. The study describes the development of a pheromone biosynthesis-activating neuropeptide (PBAN) radioreceptor assay and demonstrates the presence of a putative PBAN binding site on the pheromone gland. It also describes synthesis of a radioligand and optimization of binding conditions with respect to membrane preparation, number of gland equivalents, kinetics of ligand binding and composition of the binding solution. Binding was found to be optimal when membranes were freshly prepared from frozen glands, incubated at a concentration of one gland equivalent per reaction tube in the presence of 10 mM HCO(3)(-) ions. Equilibrium of ligand binding was obtained after 20 min. Presence of other components such as NaCl, KCl or SH reagents did not have any effect on binding. Binding was found to be saturable, with a K(d) of 5.73 +/- 1.05 x 10(-6) M and a Bmax of 1.85 +/- 0.22 nmol/mg protein. Binding was effectively displaced by unlabeled PBAN1-33NH(2) and PBAN28-33NuEta(2) with a K(i) of 4.3 +/- 1.1 x 10(-6) M and 4.9 +/- 2.6 x 10(-6) M, respectively.     

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.     

Olfactory discrimination among sex pheromone stereoisomers: chirality recognition by pink hibiscus mealybug males

Our previous field studies suggested that the two chiral centers in the sex pheromone of pink hibiscus mealybug, Maconellicoccus hirsutus, could elicit different male responses. The chiral center in the acid moiety of the pheromone seemed to be more critical than the alcohol portion of the pheromone molecule for attractiveness. The objective of the current study was to test this hypothesis by deploying stereoisomeric blends in pheromone traps. Captures of male M. hirsutus showed that pheromone with the naturally occurring (R)-maconelliyl (S)-2-methylbutanoate and (R)-lavandulyl (S)-2-methylbutanoate [R-S configuration] was most attractive and that pheromone with the unnatural S-S configuration was less attractive. In addition, the RS-R blend (containing R-R and S-R stereoisomers) yielded captures of male M. hirsutus that were comparable to blank controls, and an inhibitory effect was observed when R-R and S-R were combined with naturally occurring R-S blend. These results suggest a unique chirality recognition mechanism; olfactory discrimination among different pheromone stereoisomers depends upon both asymmetric centers. The S configuration on the acid moiety elicits attraction, whereas the R configuration induces inhibition. However, the attractive activity shows some degree of tolerance toward chirality change in the alcohol portion of the pheromone molecules.     

Scoliopteryx libatrix (L.) (Lep., Noctuidae) male reaction to the synthetic main sex pheromone component and its isomers – wind tunnel and field investigations

Abstract: The four stereoisomers of 6,13-methylheneicosene were tested with Scoliopteryx libatrix (L.) males in a wind tunnel. The most active isomer was (Z6,S13)-methylheneicosene which had been identified as the main sex pheromone component of the species. Some medium activity was found for (Z6,R13)- and (E6,S13)-, while the (E6,R13)-stereoisomer showed the lowest activity. These results were confirmed in field tests with sticky traps. Monitoring of S. libatrix at two sites showed that the flight of the insects started at the end of March to the beginning of April and lasted till August to the beginning of September. It was concluded that the males of the second generation were not attracted by the pheromone.     

Stereochemical studies of chiral resolving agents, M9PP and H9PP acids

The stereoselective Grignard reaction of (1R,2S,5R)-(-)-2-isopropyl-5-methylcyclohexyl pyruvate (menthyl pyruvate) with 9-phenanthrylmagnesium bromide yielded diastereomeric hydroxy-esters, where intramolecular OH em leader O=C hydrogen bond was observed in IR and (1)H NMR spectra. The alkaline hydrolysis of the major product gave (+)-2-hydroxy-2-(9-phenanthryl)propionic acid (H9PP acid (3)), whose absolute configuration was assigned as S based on the chemical correlation with (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl ester of (S)-2-methoxy-2-(9-phenanthryl)propionic acid (M9PP acid (2)); the absolute configuration of 2 had been previously established by X-ray crystallography. The enantioresolution of (+/-)-6-methyl-5-hepten-2-ol, sulcatol, an insect pheromone, was carried out using (S)-(+)-M9PP acid 2.     

槐庶尺蛾性信息素腺体EAG活性成分绝对构型的鉴定(英文)

槐庶尺蛾Semiothisa cinerearia Bremer et Grey （鳞翅目： 尺蛾科）是我国北方国槐Sophora japonica L.上的重要食叶害虫。本研究的主要目的是阐明槐庶尺蛾性信息素成分化学结构的绝对构型, 为在城市地区环境友好地防控槐庶尺蛾的为害提供一种新方法。经与标准品比较气相色谱保留时间和质谱特征离子, 从槐庶尺蛾处女雌蛾（2-3日龄）性信息素腺体溶剂提取物中检测到顺6, 顺9-顺-3, 4-环氧-十七碳二烯烃和顺3, 顺6, 顺9-3, 6, 9-十七碳三烯烃2种成分, 在腺体中以100∶4.8±1.3 （N=12）的比例存在。槐庶尺蛾性信息素腺体提取物进一步经手性毛细管色谱柱（CycloSil-B, 30 m×0.25 mm×0.25 μm 液膜厚）分离, 在优化的程序升温条件下发现腺体成分顺6, 顺9-顺-3, 4-环氧-十七碳二烯烃具有3R, 4S的绝对构型。两种合成的对映异构体混合物顺6, 顺9-3R, 4S-环氧-十七碳二烯烃和顺6, 顺9-3S, 4R-环氧-十七碳二烯烃以1.28∶1的比例加到腺体提取物中, 比例变为1.55∶1。根据这一分析, 腺体成分顺6, 顺9-顺-3, 4-环氧-十七碳二烯烃进一步确认具有3R, 4S的绝对构型。该研究结论将为生产上研发高效的槐庶尺蛾性信息素诱芯奠定坚实的基础。     

Synthesis of all four possible stereoisomers of 5,9-dimethylpentadecane, the major sex pheromone component of the coffee leaf miner moth, Perileucoptera coffeella

All of the four possible stereoisomers of 5,9-dimethylpentadecane, the major sex pheromone component of the coffee leaf miner moth (Perileucoptera coffeella), were synthesized by using the methyl esters of (S)- and (R)-3-hydroxy-2-methylpropanoic acid as chiral sources for the purpose of determining the stereochemistry of the pheromone.     

Synthesis of the sex pheromone of the citrus mealybug, Pseudococcus cryptus

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

蜜蜂蜂王信息素研究进展

综述了蜂王信息素的化学组成、特性、作用 ,以及与幼虫信息相互关系的研究进展 ,对蜂王信息素在养蜂和植物授粉中的应用做了介绍。西方蜜蜂的蜂王上颚腺信息素 (queen’smandibularglandpheromone,QMP)。QMP包含了 5种成分 :(E) -9-氧 -2 -癸烯酸 ( 9 ODA)、(R ,E) ( ) 和 (S,E) ( +) 9 羟基 -2 -癸烯酸 ( -9 HDA和 +9 HDA)、甲基p -羟基安息香酸盐 (HOB)、4-羟基 -3 -甲氧苯乙醇 (也称香草醇 ,HVA) ,9 ODA是其中最重要的成分 ;QMP的组分与蜜蜂的进化程度有关 ,进化程度越高则组分越复杂 ;QMP通过抑制保幼激素的产生来调节青年工蜂的个体发育。     

The pheromonal activity of chiral 3-octanol for Myrmica ants

ABSTRACT. The (R)-(-)-3-octanol from the mandibular glands of Myrmica ants is the only enantiomer active as an attractant pheromone for M.scabrinodis Nyl. The S enantiomer is inactive and its presence decreases slightly the response of M.scabrinodis to the R enantiomer. (R) and (S)-2-octanol are inactive.     

Biomimetic conversion of (3S)-(-)-neodictyoprolenol to optically pure (1S,2R)-(-)-dictyopterene B,marine algal sex pheromone

Both enantiomers of (3S)-(-)- and (3R)-(+)-Neodictyoprolenol [(3S,5Z,8Z)-(-)-1,5,8-undecatrien-3-ol] were successfully converted to the algal sex pheromone, (1S,2R)-(-)-dictyopterene B and (1R,2S)-(+)-dictyopterene B in high enantiomeric purities (e. e. > 99%), respectively, by the biomimetic reaction involving phosphorylation and elimination under a mild condition.     

Genetic fine-structural analysis of the Saccharomyces cerevisiae alpha-pheromone receptor.

The alpha-pheromone receptor encoded by the STE2 gene contains seven potential transmembrane domains. Its ability to transduce the pheromone signal is thought to require the action of a G protein. As an initial step toward defining the structural features of the receptor required for its activity, we examined the phenotypic consequences of linker insertion mutations (12 bp) at 10 different sites in the STE2 gene. Three mutant classes, which correspond to three different regions of the receptor protein, were observed. 1) The two mutants affecting the C-terminal region (C-terminal mutants) were essentially wild type for mating efficiency, pheromone binding, and pheromone sensitivity. 2) The three mutants in the N-terminus mated with reduced efficiency, showed reduced pheromone binding capacity, and were partially defective in pheromone induction of agglutinin production and cell division arrest. Increased gene dosage of these N-terminal alleles suppressed their mutant phenotypes, whereas the sst2-1 mutation, which blocks adaptation to pheromone, did not result in suppression. Thus, the N-terminal mutants were apparently limited by receptor production, but not by the adaptation function SST2. 3) The five mutants in the central region containing the seven transmembrane segments (central mutants) were completely defective for mating and did not respond to pheromone, but could be distinguished by their ability to bind pheromone. Inserts in or near transmembrane domains 2 and 4 blocked pheromone binding, whereas inserts into transmembrane domains 1, 5, and 6 retained partial pheromone binding activity even though they failed to transduce a signal. The central mutants were not suppressed by increased gene dosage, and one mutant (ste2-/101) was partially suppressed by sst2-1. Furthermore, the central core mutants were also distinguished from one another in that three of the five mutants were able to partially complement the temperature sensitivity of ste2-3.