Stereoisomeric Separation of Derivatized 2-alkanols Using Gas Chromatography-Mass Spectrometry: Sex Pheromone Precursors Found in Pine Sawfly Species

Bång, Joakim; Hedenström, Erik; Anderbrant, Olle

doi:10.1080/00032719.2012.670789

Cited by 4 publications

(8 citation statements)

References 26 publications

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“…However, even a small amount (<0.2 %) of the (2S, 3R,7R)-stereoisomer inhibits the attractiveness (Anderbrant 1999;Anderbrant et al 2000). This example emphasizes the need for analytical methods that effectively separate stereoisomers of biologically-active compounds (Bång et al 2011(Bång et al , 2012 in order to interpret and understand the results of bioassays.…”

Section: Introductionmentioning

confidence: 99%

“…In this study, we used GC/MS to determine the stereoisomeric composition of 6,10,14-trimethylpentadecan-2ol and 6,10,14-trimethylpentadecan-2-one in wing extracts from seventeen species of African Bicyclus butterflies. We improved the conditions for the GC/MS analysis of (R)-transchrysanthemoyl (Bång et al 2012) and (S)-2-acetoxypropionyl derivatives (Bång et al 2011) of 6,10,14-trimethylpentadecan-2-ol, including the identification of the elution order of each stereoisomer of the alcohol.…”

Section: Introductionmentioning

confidence: 99%

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Stereoisomeric Analysis of 6,10,14-Trimethylpentadecan-2-ol and the Corresponding Ketone in Wing Extracts from African Bicyclus Butterfly Species

et al. 2014

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Gas chromatography (GC) and mass spectrometry (MS) were used to determine the stereoisomeric compositions of 6,10,14-trimethylpentadecan-2-ol and 6,10,14-trimethylpentadecan-2-one in wing extracts from 17 Bicyclus butterfly species from different regions of Africa. All samples were purified using solid phase extraction (SPE). Since some species contained both alcohol and ketone, these were separated and the ketone was reduced to the alcohol before analysis as either (R)-trans-chrysanthemoyl or (S)-2-acetoxypropionyl esters. A novel asymmetric synthesis was developed for a reference mixture of (2R/S,6S,10R)-6,10,14-trimethylpentadecan-2-ol with known composition of the eight stereoisomers. The mixture then was used as the (R)-trans-chrysanthemoyl esters to correlate each of the eight gas chromatographic peaks to a specific stereoisomer of the extracted wing compounds. Seven butterfly species showed (2R,6R,10R)-configuration of the alcohol, four species contained minute amounts of alcohol too small to determine the stereochemistry, nine species showed (6R,10R)-configuration of the ketone, and one species contained minute amounts of ketone too small to determine the stereochemistry. No other stereoisomers of alcohol or ketone could be detected in the extracts, and the quantities of the compounds in the wing extracts varied from 5 to 900 ng per sample for each species.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Stereoisomeric Analysis of 6,10,14-Trimethylpentadecan-2-ol and the Corresponding Ketone in Wing Extracts from African Bicyclus Butterfly Species

et al. 2014

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“…Purification of extracts, derivatization, and analysis. GC/MS has been previously used to determine the stereoisomeric composition of TMPD-ol and TMPD-one in wing extracts of Bicyclus butterfly species 10 , stereoisomeric composition of TMPD-one in Euglossa bees 11 and of 3,7-dimethylpentadecan-2-ol in female extracts of pine sawflies 14 , where the stereoisomers of the chiral alcohols were separated as either (R)-trans-chrysanthemoyl or (S)-2-acetoxypropionyl esters. Here we used (S)-2-acetoxypropionyl derivatization method, because it is robust and more suitable for derivatization of compounds present at low concentrations 10,14 .…”

Section: Resultsmentioning

confidence: 99%

“…The stereoisomers of TMPD-one found in males and TMPD-ol in females of A. sociella have the same configuration on chiral centres (2R,6R,10R) as 9 butterfly species of the genus Bicyclus studied earlier by Hedenström 10 and as male orchid bees of the genus Euglossa 11 . On the other hand, 3,7-dimethylpentadecan-2-ol, present in the female sex pheromone of the pine sawfly Neodiprion lecontei, has the configuration (2 S,3 S,7 S) 14 . The stereochemistry of TMPD-one and TMPD-ol in pheromones of related species of the subfamily Galleriinae (Galleria mellonella, Tirathaba mundella or Corcyra cephalonica) has not been studied so far.…”

Section: Resultsmentioning

confidence: 99%

“…To determine the stereochemistry of TMPD-ol enriched from female extract and TMPD-one enriched from male extract of A. sociella, both the pooled alcohol fraction and the reduced ketone fraction were derivatized with (S)−2-acetoxypropionyl chloride (SigmaAldrich) according to Bång 14 . Pooled extracted TMPD-ol and reduced TMPD-one were concentrated by means of evaporating solvent under a stream of argon.…”

Section: Derivatizationmentioning

confidence: 99%

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Stereochemistry of two pheromonal components of the bumblebee wax moth, Aphomia sociella

Wallin

Kalinová

Kindl

et al. 2020

Sci Rep

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the bumblebee wax moth, Aphomia sociella, is a parasite of bumblebees. in this species, males produce sexual pheromone to attract females, while females produce an aphrodisiac pheromone that initiates male courtship. Both pheromones contain 6,10,14-trimethylpentadecan-2-one (TMPD-one) and the corresponding alcohol, 6,10,14-trimethylpentadecan-2-ol (TMPD-ol) in sex specific quantities. Male sex pheromone consists of 7 components with TMPD-one as a minor one and traces of TMPD-ol. In female aphrodisiac pheromone, TMPD-ol is the major component, while TMPD-one is present in traces. Here we report on the absolute configuration of TMPD-one in male sex pheromone and TMPD-ol in female aphrodisiac pheromone of A. sociella. The configuration was determined from GC/MS of prepared (S)-acetoxypropionyl esters of TMPD-ol. TMPD-one was first reduced to the alcohol that was then derivatized with (S)-acetoxypropionyl chloride. The GC/MS data of obtained diastereoisomers were compared with synthetic standards. The absolute configuration of TMPD-one in the male pheromone was (6R,10R). The configuration of TMPD-ol in the female pheromone was (2R,6R,10R). Electrophysiological experiments showed that TMPD-one and TMPD-ol are perceived by both sexes. the synthetic standards of naturally produced stereoisomers elicited higher responses than mixtures of all stereoisomers. The stereochemistry plays an important role in the pheromone communication 1. Therefore, it is of great importance to determine the stereoisomeric composition of pheromonal components. Aphomia sociella L. (Pyralidae, Galleriinae) is a parasite of bumblebees. Unlike most Lepidoptera, the reproductive behavior of A. sociella is initiated by males and except chemical communication (sex pheromone) it includes also an ultrasonic part. The male sex pheromone attracts females from a distance, while ultrasonic signaling urges females to accept mating 2. Females produce aphrodisiac pheromone, which initiates male courtship behavior 3. Male pheromone is a multicomponent blend consisting of (Z)-nona-2,6-dien-4-olide and mellein as major components, and 1-hexanol, 2-phenylethanol, (Z)-nona-6-en-4-olide, and 6,10,14-trimethylpentadecan-2-one (TMPD-one, trivial names phytone or hexahydrofarnesylacetone) as minor components 4,5. In female aphrodisiac pheromone, 6,10,14-tri methylpentadecan-2-ol (TMPD-ol) represents the major component with TMPD-one and hexan-1-ol as minor ones 3. TMPD-one has been found earlier within male sex pheromone of other Galleriinae, such as Galleria mellonella 6 and Tirathaba mundella 7. TMPD-ol plays a role in the communication of another species of this family, Corcyra cephalonica, where females utilize TMPD-ol for attracting males 8. Both TMPD-one and TMPD-ol are chiral compounds, but in none Galleriinae species, the absolute configuration has been reported. The stereochemistry of these two compounds was determined in other insects beside Galleriinae. TMPD-ol in Bicyclus butterflies has been determined after (S)-2-acetoxypropionyl derivatization and the f...

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Total synthesis of four stereoisomers of methyl 4,8,12-trimethylpentadecanoate, a major component of the sex pheromone of the stink bug Edessa meditabunda

2020

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Stereoisomeric Separation of Derivatized 2-alkanols Using Gas Chromatography-Mass Spectrometry: Sex Pheromone Precursors Found in Pine Sawfly Species

Cited by 4 publications

References 26 publications

Stereoisomeric Analysis of 6,10,14-Trimethylpentadecan-2-ol and the Corresponding Ketone in Wing Extracts from African Bicyclus Butterfly Species

Stereoisomeric Analysis of 6,10,14-Trimethylpentadecan-2-ol and the Corresponding Ketone in Wing Extracts from African Bicyclus Butterfly Species

Stereochemistry of two pheromonal components of the bumblebee wax moth, Aphomia sociella

Total synthesis of four stereoisomers of methyl 4,8,12-trimethylpentadecanoate, a major component of the sex pheromone of the stink bug Edessa meditabunda

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