Synthesis Of Insect Pheromones Research Articles

Recent advances in the synthesis of insect pheromones: an overview from 2013 to 2022.

Covering: 2013 to June 2022Pheromones are usually produced by insects in sub-microgram amounts, which prevents the elucidation of their structures by nuclear magnetic resonance (NMR). Instead, a synthetic reference material is needed to confirm the structure of the natural compounds. In addition, the provision of synthetic pheromones enables large-scale field trials for the development of environmentally friendly pest management tools. Because of these potential applications in pest control, insect pheromones are attractive targets for the development of synthetic procedures and the synthesis of these intraspecific chemical messengers has been at the core of numerous research efforts in the field of pheromone chemistry. The present review is a quick reference guide for the syntheses of insect pheromones published from 2013 to mid-2022, listing the synthesized compounds and highlighting current methodologies in organic synthesis, such as carbon-carbon coupling reactions, organo-transition metal chemistry including ring-closing olefin metathesis, asymmetric epoxidations and dihydroxylations, and enzymatic reactions.

Preparation of stereochemically pure E- and Z-alkenoic acids and their methyl esters from bicyclo[n.1.0]alkan-1-ols. Application in the synthesis of insect pheromones

Oxidative cleavage of exo- and endo-alkyl- and hydroxyalkyl-substituted bicyclo[n.1.0]alkan-1-ols with (diacetoxy-λ3-iodanyl)benzene gave the corresponding methyl alkenoates exclusively with E or Z configuration of the double bond. This reaction was used as the key stage in the syntheses of stereoisomerically pure components of pest insect pheromones: (E)-dodec-9-en-1-yl acetate (European pine shoot moth Rhyacionia buoliana), (Z)-tetradec-11-en-1-yl acetate (European oak leafroller Tortrix viridana), and (3E,8Z,11Z)-tetradeca-3,8,11-trien-1-yl acetate (tomato leafminer Tuta absoluta).

Cyclopropanol methodology in the synthesis of (4R)- and (4S)-4-methyltetrahydro-2H-pyran-2-ones. Application in the synthesis of insect pheromones with methyl-branched carbon skeleton

A number of chiral methyl-branched building blocks have been synthesized starting from (4S)-4-methyltetrahydro-2H-pyran-2-one, and the possibility for using them for the preparation of mealworm beetle, rhinoceros beetle, and earth-boring dung beetle pheromones and many other biologically active compounds has been demonstrated.

Ozonolysis of Unsaturated Compounds in the Synthesis of Insect Pheromones and Juvenoids

Research from the last 20 years on the use of ozonolysis of cyclic and acyclic mono- and dienes and aromatic compounds in various steps of the total synthesis of insect pheromones and juvenoids was reviewed.

Cyclopropane intermediates in the synthesis of chiral alcohols with methyl-branched carbon skeleton. Application in the synthesis of insect pheromones

Several chiral building blocks, (2R)-2-methylundec-10-en-1-ol, (3R)-3-methylheptan-1-ol, and (4R)-4-methyloctan-1-ol, have been synthesized using cyclopropane intermediate products. It has been shown that the obtained chiral alcohols can be used in the synthesis of insect pheromones.

(3S,5R)-6-(benzyloxy)-3-methylhexane-1,5-diol in the synthesis of insect pheromones with methyl-branched carbon chain and of amphidinolide L C 7 –C 14 fragment

New building block (3S,5R)-6-(benzyloxy)-3-methylhexane-1,5-diol was obtained, and based thereon new formal syntheses of (Z)-trogodermal, a component of the sex pheromone of smaller tea tortrix and of the alarm pheromone of ants of genus Crematogaster were suggested. A new synthetic protocol for (3S)-5-methyl-5-oxopentyl acetate and (3S)-5-(benzyloxy)-3-methylpentanal, convenient building blocks for insect pheromones designing was developed. A new simple and efficient asymmetric synthesis of C7–C14 fragment of the cytotoxic macrolactone amphidinolide L was carried out.

(4R,6R)-6-(hydroxymethyl)-4-methyltetrahydro-2H-pyran-2-one in the synthesis of polyfunctional compounds with the methyl-branched carbon skeleton

A simple and efficient asymmetrical synthesis was performed of a convenient bifunctional building block, methyl (R)-5,5-dimethoxy-3-methylpentanoate and its (S)-enantiomer. The possibility was shown of its application to the synthesis of insect pheromones.

Synthesis of insect pheromones: Improved method for the preparation of queen substance and royal jelly of honeybees Apis mellifera

The biological activity of pheromones stems from various applications, especially in the area of pest control and insect monitoring; however, the quantity of pure pheromones available from natural sources is often extremely limited, because individual insects contain only minute amounts of pheromone. As our contribution to the field of pheromone synthesis, here we present a novel approach for the preparation of two known pheromones, namely queen substance and royal jelly of honeybees Apis mellifera. Our method is based on the original applications of lithiated α-alkenylphosphoramido anions as excellent synthetic equivalents of homoenolate anions.

Copper-catalyzed cross-coupling of (Z)-allyl phenyl ethers with Grignard compounds in the synthesis of insect pheromones

(8Z)-Dodec-8-en-1-yl acetate (pheromone of oriental fruit moth Grapholita molesta) and (9Z)-dodec-9-en-1-yl acetate (pheromone of grape berry moth Paralobesia viteana) containing impurities of isomeric structures were synthesized via copper-catalyzed cross-coupling of (Z)-1-phenoxyhex-2-ene and (Z)-1-phenoxypent-2-ene, respectively, with Grignard compounds in the key stage.

Furanyl spiroketals as stereochemical relays in the synthesis of 1,9- anti diols: synthesis of insect pheromones

A suite of spiroketal insect pheromones ( 15 and 17a– d) has been synthesised in good yield and with very high levels of diastereoselectivity via furanyl spiroketals. Remote asymmetric induction is achieved under thermodynamic control. The use of furanyl spiroketals as temporary scaffolds in the synthesis of 1,9- anti diols has been demonstrated with the synthesis of the swede midge pheromone (2 S,10 S)-2,10-diacetoxyundecane 1. The enzymatic resolution of a C 2 symmetric 1,9- anti diol was used as a confirmation of diastereomeric purity.

Hydrolytic kinetic resolution of terminal mono- and bis-epoxides in the synthesis of insect pheromones: routes to (−)-(R)- and (+)-(S)-10-methyldodecyl acetate, (−)-(R)-10-methyl-2-tridecanone, (−)-(R)-(Z)-undec-6-en-2-ol (Nostrenol), (−)-(1R,7R)-1,7-dimethylnonyl propanoate, (−)-(6R,12R)-6,12-dimethylpentadecan-2-one, (−)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane

Hydrolytic kinetic resolution (HKR) of functionalised epoxides using (salen)Co(OAc) complexes provides enantiomerically enriched epoxides and diols, which have been transformed into important insect sex pheromones. In this general approach, (−)-(R)- and (+)-(S)-10-methyldodecyl acetates from the smaller tea tortrix moth were obtained, as was (−)-(R)-10-methyltridecan-2-one from the southern corn rootworm. The (S)-epoxide obtained from undec-1-en-6-yne was transformed to (−)-(R)-(Z)-undec-6-en-2-ol (Nostrenol) from ant-lions. HKR of appropriate bisepoxides was also investigated, and transformations of the resulting bisepoxides and epoxydiols provided (−)-(1R,7R)-1,7-dimethylnonylpropanoate from corn rootworms, (−)-(6R,12R)-6,12-dimethylpentadecan-2-one from the female banded cucumber beetle, and (−)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane from female pea-midges.

Stereospecific 1,4-cis-hydrogenation of conjugated dienes, dienynes, and dienediynes catalyzed by chromium carbonyl complexes in stereocontrolled syntheses of physiologically active olefins

Synthesis of insect pheromones provides a good illustration of versatility, flexiblility, and practical convenience of the chromium carbonyl complexes-mediated 1,4-cis-hydrogenation of conjugated dienes as the tool for for stereocontrolled construction of di-, tri-, and tetrasubstituted olefins and nonconjugated dienes. A new strategy for synthesizing homoconjugated all-Z-dienes and trienes by hydrogenation of diene-alkyne conjugated systems using the same catalysts is proposed.

ChemInform Abstract: Hydrolytic Kinetic Resolution of Mono‐ and Bisepoxides as a Key Step in the Synthesis of Insect Pheromones.

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Hydrolytic kinetic resolution of mono- and bisepoxides as a key step in the synthesis of insect pheromones

The synthetic utility of the readily separated epoxides, diols, epoxydiols and tetrols of high enantiomeric excesses, obtained by hydrolytic kinetic resolution (HKR) of functionalised mono- and bisepoxides with (salen)Co(OAc) complexes, is demonstrated by their efficient transformations to important insect pheromones.

IMPROVED HORNER-WADSWORTH-EMMONS PREPARATION OF α-METHYL- OR α-ETHYL-α,β-UNSATURATED ESTERS FROM ALDEHYDES

The E-isomer selectivity of the Horner-Wadsworth-Emmons olefination of aldehydes to form α-methyl- or α-ethyl-α,β-unsaturated esters has been improved by using lithium tert-butoxide as the base, triethyl-2-phosphonopropionate or triethyl-2-phospho-nobutyrate as the phosphonate, an aldehyde, and hexane as the reaction solvent. Greater E-isomer selectivity was observed in the formation of α-methyl-α,β-unsaturated esters than α-ethyl-α,β-unsaturated esters. These compounds are useful intermediates for the synthesis of insect pheromones and natural products.

ChemInform Abstract: Synthesis of Insect Pheromones Belonging to the Group of (Z)-Trisubstituted Alkenes

ChemInform Abstract: Synthesis of Insect Pheromones Belonging to the Group of (Z)-Trisubstituted Alkenes

10-Undecenoic acid in the synthesis of insect pheromones

The literature on the use of 10-undecenoic acid in the synthesis of insect pheromones is reviewed.

Use of enyne compounds in the synthesis of insect pheromones

A new approach has been developed to the synthesis of monogenic insect pheromones with acetogenin and macrolide structures, using the low reactivity of ozone and of 9-borabicyclo[3.3.1]nonane towards an acetylenic function as compared with a vinyl function.

Book Review: The Synthesis of Insect Pheromones, 1979–1989. (Series: The Total Synthesis of Natural Products, Vol: 9. Series editor: J. ApSimon.) By K. Mori

Book Review: The Synthesis of Insect Pheromones, 1979–1989. (Series: The Total Synthesis of Natural Products, Vol: 9. Series editor: J. ApSimon.) By K. Mori

Structural elucidation and chiral syntheses of insect pheromones and extension of the synthetic approaches

Abstract