Resolution of Pheromonal Epoxydienes by Chiral HPLC, Stereochemistry of Separated Enantiomers, and Their Field Evaluation

Qin, Xurong; Ando, Tetsu; Yamamoto, Masanobu; Yamashita, Manabu; Kusano, Kazutaka; Abé, Hiroshi

doi:10.1023/b:joec.0000006472.12370.c6

Cited by 18 publications

(7 citation statements)

References 15 publications

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“…Even with a standard analytical column, tens of micrograms can be obtained, which is usually sufficient for bioassay and field testing. For cecidomyiid pheromone components, the most widely used system has been a normal phase Chiralpak AD column (Diacel Chemical Industry Co. Ltd., Tokyo, Japan), eluted with hexane modified with a small amount of 2-propanol, as developed by Qin et al (1997) for chiral moth pheromones. This was used to separate enantiomers of pheromones with one chiral center for field testing (Table 1, entries 15 and 16), and has proved particularly useful for separation of all stereoisomers of compounds with two chiral centers, which are much more difficult to synthesize (Table 1, entries 7, 11, 13, 14).…”

Section: Synthesis Of Pheromone Componentsmentioning

confidence: 99%

The Chemical Ecology of Cecidomyiid Midges (Diptera: Cecidomyiidae)

et al. 2012

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The family of cecidomyiid midges (Diptera: Cecidomyiidae) exhibits diversified patterns of life history, behavior, host range, population dynamics and other ecological traits. Those that feed on plants include many important agricultural pests; most cultivated plants are attacked by at least one midge species. Several features of the reproductive biology of cecidomyiid midges point to an important role for chemical communication, with this topic last reviewed comprehensively 12 years ago. Here, we review progress on identification of sex pheromones, chemicals involved in location of host plants, the neurophysiology of reception of volatile chemicals, and application of semiochemicals to management of pest species of cecidomyiid midges that has occurred during the last decade. We hope this review will stimulate and sustain further research in these fields.

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Section: Synthesis Of Pheromone Componentsmentioning

confidence: 99%

The Chemical Ecology of Cecidomyiid Midges (Diptera: Cecidomyiidae)

et al. 2012

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“…This epoxidation proceeds without regio-selectivity and mixtures of three epoxydienes and two epoxymonoenes are produced from the trienes and dienes, respectively. When the epoxydiene mixture is injected into a Lobar column of MPLC, the positional isomers separately elute in the order of 6,7-, 9,10-, and 3,4-epoxydienes [179]. This MPLC separation is better than that of HPLC with an ODS column, which performs the elution in a different order of 9,10-, 3,4-, and 6,7-epoxydienes (see Fig.…”

Section: Separation With a Chiral Columnsmentioning

confidence: 99%

“…The resolution abilities of chiral HPLC columns have been examined in detail, as shown in Table 7 and Fig. 14 [75,76,179]. The Chiralpak AD column operated under a normal-phase condition separates well two enantiomers of 9,10-epoxydienes, 6,7-epoxymonoenes and 9,10-epoxymonoenes.Another normal-phase column, the Chiralpak AS column, is suitable for the resolution of the 3,4-epoxydienes.…”

Section: Enantiomeric Separation With Chiral Columnsmentioning

confidence: 99%

“…Examining the 1 H NMR data of esters of the produced methoxyalcohols with (S)-and (R)-a-methoxy-a-(trifluoromethyl) phenylacetic acid by a modified Mosher's method [181], it has been indicated that the earlier eluting parent epoxides are (3S,4R)-, (6S,7R)-, and (9R,10S)-isomers (Table 7) [75,76,179]. The above three chiral HPLC columns show different resolution abilities but a different elution order is not observed.…”

Section: Enantiomeric Separation With Chiral Columnsmentioning

confidence: 99%

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Lepidopteran Sex Pheromones

Ando

Inomata

Yamamoto

2004

Topics in Current Chemistry

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332

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As a consequence of the diversity of Lepidoptera, including 150,000 described species, interesting species-specific sex pheromone systems are exhibited in this insect group. The quite varied pheromones, which have been identified from female moths of nearly 530 species from around the world, are classified into groups of Type I (75%), Type II (15%), and miscellaneous (10%), according to their chemical structures. Additionally, many pheromones produced by male moths and butterflies have been known. While new sex pheromones from about 70 lepidopteran species have been reported in the last five years utilizing GC-EAD, GC-MS, LC, and NMR, our information about the pheromones is still rudimentary, and these kinds of semiochemicals remain an exciting research target for natural product chemistry. In addition to the overview of their chemical structures, this chapter deals with current methods for their identification. Furthermore, an actual application of the synthetic pheromones for pest control is briefly introduced.

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“…3). In our pheromone research, the chiral HPLC has been used for the resolution of several epoxy compounds in lepidopteran Type II pheromones (Qin et al 1997;Yamamoto et al 1999;Ando et al 2004), an acetate of secondary alcohol produced by a midge (Hall et al 2009), and a ketol and a diol produced by a long-horned beetle (Kiyota et al 2009). This study is the first successful application of chiral HPLC to methyl-branched pheromones, and it is noteworthy that enantiomers of less polar volatiles showed different chromatographic behaviors on a chiral HPLC column.…”

Section: Discussionmentioning

confidence: 99%

Positions and Stereochemistry of Methyl Branches in the Novel Sex Pheromone Components Produced by a Lichen Moth, Lyclene dharma dharma

et al. 2010

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Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce three sex pheromone components (I-III), for which we assigned the following novel chemical structures; 6-methyl-2-octadecanone (1) for I, 14-methyl-2-octadecanone (2) for II, and 6,14-dimethyl-2-octadecanone (3) for III. In the Iriomote Islands where the insects were collected, a lure including racemic 1 and 2 attracted the male moths without mixing 3. In this study for further confirmation of the plane structures, the positional isomers with a methyl branch at the 4-, 5-, 7-, 13-, or 15-position (4-8, respectively) were synthesized. The GC-MS analyses revealed that natural components I and II were best fitted with those of 1 and 2, respectively, among the methyl-2-octadecanones examined, indicating the usefulness of this analytical instrument and authentic standards for the determination of the positions of methyl branches. In field trapping tests, 4-8 could not substitute for 1 or 2, nor did these compounds inhibit the active binary lure of 1 and 2, indicating that the males strictly recognized the 2-ketones with a methyl branch at the 6- or 14-positions. Next, the absolute configurations of I and II were determined by HPLC with a normal-phased chiral column (Chiralpak AD-H), which could separate the enantiomers of both 1 and 2. The chiral HPLC analysis of a crude pheromone extract indicated that the females exclusively produced (S)-1 and (S)-2. Furthermore, a field evaluation of each enantiomer revealed that (S)-1 and (S)-2 were bioactive but (R)-1 and (R)-2 were not.

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Resolution of Pheromonal Epoxydienes by Chiral HPLC, Stereochemistry of Separated Enantiomers, and Their Field Evaluation

Cited by 18 publications

References 15 publications

The Chemical Ecology of Cecidomyiid Midges (Diptera: Cecidomyiidae)

The Chemical Ecology of Cecidomyiid Midges (Diptera: Cecidomyiidae)

Lepidopteran Sex Pheromones

Positions and Stereochemistry of Methyl Branches in the Novel Sex Pheromone Components Produced by a Lichen Moth, Lyclene dharma dharma

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