A Concise, Efficient and Flexible Strategy for the Synthesis of the Pheromones of<i>Oryzaephilus</i>and<i>Cryptolestes</i>Grain Beetles

Boden, Christopher D. J.; Chambers, J.; Stevens, I. D. R.

doi:10.1055/s-1993-25874

Cited by 23 publications

(22 citation statements)

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“…The Oehlschlager synthesis10, 11 of 5 was improved by Boden et al 8. They reported a new approach for the synthesis of a hydroxy acid precursor based on a Wittig olefination.…”

Section: Resultsmentioning

confidence: 99%

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Identification and Synthesis of Macrolide Pheromones of the Grain Beetle Oryzaephilus Surinamensis and the Frog Spinomantis Aglavei

Hötling

Haberlag

Tamm

et al. 2014

Chemistry A European J

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Macrolide lactones, the so called cucujolides derived from unsaturated fatty acids, are aggregation pheromones of cucujid grain beetles. Thirty years ago, Oehlschlarger et al. showed that (3Z,6Z)-dodeca-3,6-dien-11-olide (4) and the respective 12-olide (7) attract the sawtoothed grain beetle Oryzaephilus surinamensis, whereas (5Z,8Z,13R)-tetradeca-5,8-dien-13-olide (5) increases the response synergistically. The frass of this beetle is attractive for its parasitoid Cephalonomia tarsalis, which potentially can be used for pest control. A GC/MS analysis of attractive frass showed the presence of 5, together with an unknown isomer. Cucujolide V was tentatively identified also in the femoral glands, pheromone-releasing structures, of the Madagascan mantelline frog Spinomantis aglavei. Therefore, a new route to synthesize doubly unsaturated macrolides allowing the flexible attachment of the side chain was developed. A straightforward method to obtain Z configured macrolides involves ring-closing alkyne metathesis (RCAM) followed by Lindlar-catalyzed hydrogenation. This methodology was extended to homoconjugated diene macrolides by using RCAM after introduction of one Z configured double bond in the precursor by Wittig reaction. A tungsten benzylidyne complex was used as the catalyst in the RCAM reaction, which afforded the products in high yield at room temperature. With the synthetic material at hand, the unknown isomer was identified as the new natural product (5Z,8Z,12R)-tetradeca-5,8-dien-12-olide, cucujolide X (8). Furthermore, the route also allowed the synthesis of cucujolide V in good yield. The natural products were identified by the synthesis of enantiomerically pure or enriched material and gas chromatography on chiral phases. The new macrolide (R)-8 proved to be biologically active, attracting female O. surinamensis, but no males. The synthetic material allowed the identification of (R)-5 in both the beetle and the frog.

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“…The Oehlschlager synthesis10, 11 of 5 was improved by Boden et al 8. They reported a new approach for the synthesis of a hydroxy acid precursor based on a Wittig olefination.…”

Section: Resultsmentioning

confidence: 99%

“…O. surinamensis is one of the most common pests in stored grain worldwide 8. The application of insecticides in stored grain is problematic because of residues remaining on the grain.…”

Section: Introductionmentioning

confidence: 99%

Identification and Synthesis of Macrolide Pheromones of the Grain Beetle Oryzaephilus Surinamensis and the Frog Spinomantis Aglavei

Hötling

Haberlag

Tamm

et al. 2014

Chemistry A European J

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“…The residue was purified by column chromatography (50:1 n-pentane/EtOAc) to give 1 as colorless oil ( 4.1.11. 3b-(tert-Butyldimethylsilyloxy)-11a-(7-ethoxycarbonylhept-1-yl)-vitamin D 3 (17). A solution of 16 23 (455 mg, 1.01 mmol) in dry THF (1 mL) was added slowly to a solution of n-BuLi (0.63 mL, 1.01 mmol, 1.6 M) in dry THF (1 mL) at À78 C under N 2 .…”

Section: General Materials and Methodsmentioning

confidence: 99%

Synthesis of C-11 linked active ester derivatives of vitamin D3 and their conjugations to 42-residue helix–loop–helix peptides

et al. 2010

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“…105,108 Recently, a new cucujolide, (5Z,8Z,12R)-tetradeca-5,8-dien-12-olide (cucujolide X, 91), was identied and shown to induce attraction of both sexes of the sawtoothed grain beetle, Oryzaephilus surinamensis, 109 which is one of the most common pests in stored grain. 110 The biosynthesis of these pheromones has been examined in the rusty grain beetle, C. ferrugineus and in the merchant grain beetle, O. mercator, using radiolabeled precursors. 108 The biosynthesis of 85 starts from oleic acid (42), followed by three cycles of b-oxidation to acid 92, and hydroxylation at the u-1 carbon atom to precursor 93.…”

Section: Larger Macrocyclic Lactonesmentioning

confidence: 99%

“…14) started from 10-bromo-1-decene which was transformed into the aldehyde 102 and coupled in a lithium- Fortunately, both macrocyclic lactones were active against the ash borer, so the blend of 2 : 1 had the potential to be a detection, mating disruptor or mass trapping agent, which could be used in emerald ash borer control. A related macrocyclic lactone, parcoblattalactone (110), is a sex pheromone of the broad wood cockroach, Parcoblatta lata, 122 found in the pine forests of southeastern USA. The 13-membered (3Z,10Z)-dodeca-3,10-dienolide (110) was synthesized by cyclization of the diyne precursor 108 and subsequent hydrogenation (Fig.…”

Section: Larger Macrocyclic Lactonesmentioning

confidence: 99%

The use of the lactone motif in chemical communication

Schulz

Hötling

2015

Nat. Prod. Rep.

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A wide variety of organisms communicate via the chemical channel using small molecules. A structural feature quite often found is the lactone motif. In the present paper, the current knowledge on such lactones will be described, concentrating on the structure, chemistry, function, biosynthesis and synthesis of these compounds. Lactone semiochemicals from insects, vertebrates and bacteria, which this article will focus on, are particularly well investigated. In addition, some ideas on the advantageous use of lactones as volatile signals, which promoted their evolutionary development, will be discussed.

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A Concise, Efficient and Flexible Strategy for the Synthesis of the Pheromones ofOryzaephilusandCryptolestesGrain Beetles

Cited by 23 publications

References 0 publications

Identification and Synthesis of Macrolide Pheromones of the Grain Beetle Oryzaephilus Surinamensis and the Frog Spinomantis Aglavei

Identification and Synthesis of Macrolide Pheromones of the Grain Beetle Oryzaephilus Surinamensis and the Frog Spinomantis Aglavei

Synthesis of C-11 linked active ester derivatives of vitamin D3 and their conjugations to 42-residue helix–loop–helix peptides

The use of the lactone motif in chemical communication

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