Oviposition Attractant Pheromone Research Articles

Facile total synthesis of (−)-(5R,6S)-6-acetoxy-5-hexadecanolide from carbohydrate, a mosquito oviposition attractant pheromone

Total synthesis of (−)-(5R,6S)-6-acetoxy-5-hexadecanolide, a major component of mosquito oviposition attractant pheromones is reported. The key synthetic steps involve epoxide opening by lithiated salt of ethylpropionate and acid catalysed lactonization. The total synthesis was achieved in 11 linear steps staring from a readily available carbohydrate δ-gluconolactone in 18% overall yield making it simple, practical and elegant.

A Facile Synthesis of Both Enantiomers of 6‐Acetoxy‐5‐hexadecanolide, a Major Component of Mosquito Oviposition Attractant Pheromones

AbstractThe stereoselective synthesis of (–)‐(5R,6S)‐erythro‐6‐acetoxy‐5‐hexadecanolide, the major component of a mosquito oviposition attractant pheromone, and its enantiomer are reported. The synthesis was completed over seven steps in 28 % overall yield by using Sharpless asymmetric epoxidation and ZrCl4‐catalyzed cyclic acetal formation as the key steps. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Synthesis of (−)-(5 R,6 S)-6-acetoxyhexadecanolide based on l-proline-catalyzed asymmetric aldol reactions

A convenient method for proline-catalyzed asymmetric aldol reactions using synthons of straight-chain aliphatic aldehydes, and aldehydes bearing a 1,3-dithiane moiety at the β-position, has been developed. This method was successfully applied to the synthesis of (−)-(5 R,6 S)-6-acetoxyhexadecanolide, an oviposition attractant pheromone of the female Culex mosquito.

3‐Boronoacrolein as an Exceptional Heterodiene in the Highly Enantio‐ and Diastereoselective Cr(III)‐Catalyzed Three‐Component [4 + 2]/Allylboration.

AbstractFor Abstract see ChemInform Abstract in Full Text.

3-Boronoacrolein as an exceptional heterodiene in the highly enantio- and diastereoselective Cr(III)-catalyzed three-component [4+2]/allylboration.

This Communication reports the optimization of the first catalytic enantio- and diastereoselective hetero[4+2]/allylboration reaction to provide efficient access to alpha-hydroxyalkyl pyran derivatives. The key substrate 3-boronoacrolein pinacolate appears to be an exceptionally favorable heterodiene for use in Jacobsen's enantioselective reverse electron demand hetero[4+2] reaction with enol ethers, catalyzed by the tridentate (Schiff base)chromium complex 1. This one-pot three-component reaction was successfully applied to a concise total synthesis of (5R,6S)-6-acetoxy-5-hexadecanolide (2), the oviposition attractant pheromone of the female Culex mosquito capable of transmitting the West Nile virus.

A Ru catalyzed divergence: oxidative cyclization vs cycloisomerization of bis-homopropargylic alcohols.

During the course of investigating the development of catalytic reactions involving ruthenium vinylidene intermediates, a novel divergence of reactivity was discovered. The oxidative cyclization of bis-homopropargylic alcohols with Ru(+2) complexes as catalysts and N-hydroxysuccinimide as oxidant, which requires formation of a ruthenium vinylidene intermediate, is complicated by the simple electrophilically initiated direct attack of the hydroxyl group on a pi-complex of the alkyne and ruthenium. A catalytic system composed of CpRu[(p-CH(3)O(6)H(4))(3)P](2)Cl and excess (p-CH(3)O-C(6)H(4))(3)P directs the reaction toward the oxidative cyclization to form delta-lactones in good yields. Significantly, a simple switch of catalyst to CpRu[(p-FC(6)H(4))(3)P](2)Cl redirects the reaction to a cycloisomerization to form dihydropyrans in good yields. The synthetic utility of the oxidative cyclization is illustrated by the synthesis of oviposition attractant pheromone of the mosquito Culex pipens. The utility of the cycloisomerization to dihydropyrans is demonstrated by an iterative process leading to the antiviral agent narbosine B. A rationale for this dramatic switch by simple ligand modification is proposed.

Intramolecular S N2 ring opening of a cyclic sulfate: synthesis of erythro-(−)-6-acetoxy-5-hexadecanolide—a major component of mosquito oviposition attractant pheromone

Methyl trans-hexa-5-decenoate is dihydroxylated using AD-mix-α followed by treatment with thionyl chloride to furnish cyclic sulfite 8 as the major product. The cyclic sulfite 8 is oxidized to the cyclic sulfate 2. Highly regio- and stereospecific ring opening of (4 S,5 S)-carboxybutyl-5-decylcyclic sulfate generated in situ by the hydrolysis of 2 furnished (5 R,6 S)-6-hydroxy-5-hexadecanolide, 9 in high yield. Acetylation of 9 afforded natural oviposition attractant pheromone 1 in good yield.

Enzymes in organic synthesis. 27. Lipase-Catalyzed Synthesis of (5R,6S)-6-Acetoxyalkan-5-olides - homologues of the mosquito oviposition attractant pheromone

Sixteen homologous (5R*,6S*)-6-hydroxyalkan-5-olides rac-5 and their acetoxy derivatives rac-6 were synthesized from the corresponding methyl (Z)-alk-5-enoates 3 by osmium(VIII) oxide catalyzed cis-hydroxylation to the dihydroxy esters rac-4 and hydrolysis of these esters followed by lactonization. Pancreatin-catalyzed lactonization of the dihydroxy esters rac-4 afforded enantiomerically enriched hydroxy lactones ent-5, five of which were obtained enantiomerically pure by recrystallization. Acetylation of the 6-hydroxyalkan-5-olides rac-5 by vinyl acetate catalyzed by the lipase SP 526 provided enantiomerically enriched 6-acetoxyalkan-5-olides 6 with an enantiomeric excess of more than 90% in nine cases. These compounds are known as mosquito oviposition attractant pheromone (6h) or its homologues.

Syntheses of Chiral Acyclic Natural Products from Sugar

AbstractThe syntheses of several biologically interesting acyclic natural products such as LTA, 1, LTB4 8, mosquito oviposition attractant pheromone 46 and cytotoxic annonaceous acetogenin corossolone 57 and corossoline 58 from sugars in our laboratory are reviewed.

Enzymes in organic synthesis, 23. Chemo‐enzymatic synthesis of (5R,6S)‐6‐acetoxyhexadecan‐5‐olide — the major component of the mosquito oviposition attractant pheromone

AbstractThe methyl ester rac‐4a of (5R*,6S*)‐5,6‐dihydroxyhexadecanoic acid was prepared by a Wittig reaction of (4‐carboxybutyl)triphenylphosphonium bromide (2) with undecanal (1) followed by esterification with methanol and cis dihydroxylation with osmium (VIII) oxide/N‐methylmorpholine N‐oxide. After conversion of the dihydroxy ester rac‐4a into (5R*,6S*)‐6‐hydroxyhexadecan‐5‐olide (rac‐5) by lactonization (5R,6S)‐6‐acetoxyhexadecan‐5‐olide (6), the mosquito oviposition attractant pheromone, was obtained by an enantioselective lipase‐catalyzed acetylation with vinyl acetate. In an alternative route the dihydroxy ester rac‐4a was subjected to a lipase‐catalyzed lactonization, which afforded as the main product (5S,6R)‐6‐hydroxyhexadecan‐5‐olide (ent‐5), the enantiomer of the deacetylated pheromone.

Enantio and stereoselective synthesis of (5R,6S)-6-acetoxy-hexadecanolide, a mosquito oviposition attractant pheromone

The enantio and stereoselective synthesis of (5R, 6S)-6-acetoxy-hexadecanolide is described via chemo, regio and stereoselective opening with LiI of a chiral epoxy alcohol precursor.

Synthesis of (-)-Muricatacin and (-)-(5 R,6 S)-6-acetoxy-5-hexadecanolide, the Mosquito oviposition attractant pheromone, from D-isoascorbic acid

From D-isoascorbic acid, a general approach to enantiomerically pure hydroxy γ-butyro and δ-valero lactones, (-)-Muricatacin and (-)-(5 R,6 S)-6-acetoxy-5-hexadecanolide, via a four carbon atoms bis-epoxide equivalent, is reported.

Stereoselective synthesis of (5R,6S)‐6‐acetoxy hexadecanolide—The major component of the oviposition attractant pheromone of the mosquito Culex pipens fatigans and its enantiomer from L‐glutamic acid

AbstractA concise synthesis of the mosquito oviposition attractant pheromone, (‐)(5R, 6S)‐and (+)‐(5S, 6R)‐6‐acetoxy hexadecanolide from L‐glutamic acid is described. The key steps are the inversion of the configuration at C‐4 of 7, and the formation of δ‐lactone from the γ‐lactone through ring enlargement.

A Concise Synthesis of the Natural Mosquito Oviposition Attractant Pheromone from D-Glucose

The major component of the oviposition attractant pheromone of the mosquito Culex pipiens fatigans was shown to be (-)-(5R, 6S)-6-acetoxy-5-hexadecanolide (1).1 For the chemical synthesis of this optically active pheromone,2 carbohydrates such as D-mannitol2i and 2-deoxy-D-ribose21 have been utilized as chiral templates. In this laboratory the natural pheromone has been synthesized from (S)- and (R)-O,O-isopropylideneglyceraldehyde independently, using diastereoselective dihydroxylation as the key step.2m We now describe an enantiospecific synthesis of the pheromone from D-glucose.

ChemInform Abstract: Diastereoselective Synthesis of (‐)‐(5R,6S)‐6‐Acetoxyhexadecan‐5‐olide.

AbstractTwo novel, short and efficient routes are reported for the synthesis of the title hexadecanolide (X), the natural mosquito oviposition attractant pheromone.

Inversion of configurations of contiguous carbinol centres: application to the synthesis of both enantiomers of natural products from the same enantiomerically pure starting material

A novel method for effecting the inversion of configuration of two and three contiguous carbinol centers in a diol, triol, and tetraol chain, thus affording the opposite enantiomer with ⩾98% e.e., has been developed. The method is based on the sequential formation of a terminal epoxide, Payne rearrangement, and intramolecular lactonization. Application of this methodology to the synthesis of a leukotriene A 4 intermediate and its enantiomer, and the oviposition attractant pheromone of the mosquito Culex pipiens fatigans and its enantiomer, from the same enantiomerically pure starting material is described 1.

Stereoselective synthesis of (-)-(5R,6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition attractant pheromone

The natural mosquito oviposition attractant pheromone,(-)-(5R,6S)- 6-acetoxy-5-hexadecanolide ( 1 ) was synthesized from readily available 1,2-cyclohexanediol, using kinetic resolution of cyclic allylic alcohol by modified Sharpless asymmetric epoxidation reagent as the key step.

ChemInform Abstract: An Enantiospecific Synthesis of (‐)‐(5R,6S)‐6‐Acetoxy‐5‐hexadecanolide (IX), the Mosquito Oviposition Attractant Pheromone.

ChemInformVolume 20, Issue 32 Natural Products ChemInform Abstract: An Enantiospecific Synthesis of (-)-(5R,6S)-6-Acetoxy-5-hexadecanolide (IX), the Mosquito Oviposition Attractant Pheromone. S.-K. KANG, S.-K. KANG Dep. Chem., Sung Kyun Kwan Univ., Nat. Sci. Campus, Suwon 440-746, KoreaSearch for more papers by this authorI.-H. CHO, I.-H. CHO Dep. Chem., Sung Kyun Kwan Univ., Nat. Sci. Campus, Suwon 440-746, KoreaSearch for more papers by this author S.-K. KANG, S.-K. KANG Dep. Chem., Sung Kyun Kwan Univ., Nat. Sci. Campus, Suwon 440-746, KoreaSearch for more papers by this authorI.-H. CHO, I.-H. CHO Dep. Chem., Sung Kyun Kwan Univ., Nat. Sci. Campus, Suwon 440-746, KoreaSearch for more papers by this author First published: August 8, 1989 https://doi.org/10.1002/chin.198932325AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume20, Issue32August 8, 1989 RelatedInformation

An enantiospecific synthesis of (-)-(5R,6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition attractant pheromone

(-)-(5R,6S)-6-Acetoxy-5-hexadecanolide, (-)-1, the natural mosquito oviposition attractant pheromone was synthesized from readily available carbohydrate, (-)-2-deoxy-d-ribose, using radical carbon-carbon bond formation as the key step.

Response of an East African Mosquito, Culex pipiens fatigans Wied to Synthetic Oviposition Attractant Pheromone in the Laboratory at Mbita Point, Kenya, East Africa

Studies have shown that the East African mosquito strain, Culex pipiens fatigans, is attracted to a synthetic oviposition attractant pheromone in the laboratory. Chemical analysis has shown that the main volatile component of the apical droplets is ( —)-(5R,6R) erythro-6-acetoxy-5-hexadecanolide. In contrast to the lack of response in the Sri Lankan strain of the same mosquito, the East African strain shows remarkable similarity in attraction response to the West African, American and Japanese strains of C p. fatigans.