- Bidirectional, organocatalytic synthesis of lepidopteran sex pheromones
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Shuffling of two simple building blocks and a regioselective transfer hydrogenation allow for the rapid synthesis of a small collection of lepidopteran sex pheromones, e.g., 8E,10Z-tetradeca-8,10-dienal 5c, from the horse chestnut leafminer (Cameraria ohridella).
- De Figueiredo, Renata Marcia,Berner, Raphael,Julis, Jennifer,Liu, Ting,Tuerp, David,Christmann, Mathias
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p. 640 - 642
(2007/10/03)
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- Syntheses of (Z,E)-5,7-dodecadienol and (E,Z)-10,12-hexadecadienol, lepidoptera pheromone components, via zinc reduction of enyne precursors. Test of pheromone efficacy against the Siberian moth
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Efficient syntheses of (Z,E)-5,7-dodecadienol, a pheromone component of the Siberian moth, Dendrolimus superans sibiricus, and (E,Z)-10,12-hexadecadienol, a pheromone component of various Lepidoptera pheromones, were accomplished by cis reduction of the corresponding enynols with activated zinc. The most energetic reagent was zinc galvanized with copper and silver (Zn/Cu/Ag) that achieved rapid and high-yield reduction in methanol-water. The stereoselectivity of semihydrogenation was ≥98%. A process whereby zinc dust was continuously activated throughout the reduction with an acid was also satisfactory (95-98% cis). Field evaluation of the 1:1 mixture of (Z,E)-5,7-dodecadienol and (Z,E)-5,7-dodecadienal with the Siberian moth in Russia showed that the rubber septa pretreated with compound and stored at -80 °C were as effective as freshly treated septa. Moth responses to septa aged in open air indicated that lure effectiveness declined significantly after 2 weeks of aging. Thus, if rubber septa are used as pheromone dispensers in Siberian moth traps monitoring, they should be replaced biweekly with fresh septa for optimal trap effectiveness.
- Khrimian, Ashot,Klun, Jerome A.,Hijji, Yousef,Baranchikov, Yuri N.,Pet'Ko, Vladimir M.,Mastro, Victor C.,Kramer, Matthew H.
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p. 6366 - 6370
(2007/10/03)
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- A facile preparation of geometrically pure alkenyl, alkynyl, and aryl conjugated Z-alkenes: Stereospecific synthesis of bombykol
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Ni- and Pd-catalyzed cross coupling reactions of 2-alkenyl, 2-alkynyl, and 2-aryl substituted (1Z)-1-bromoalkene with alkyl Grignard reagents gave 1-alkyl substituted (1Z,3E)-diene, (1Z)-en-3-yne, and (1Z)-2-arylethene, each in good yield. When (trimethylsilyl)-methylmagnesium chloride was used as the Grignard reagent, conjugated Z-allylsilane was produced. Bombykol, (10E, 12Z)-10,12-hexadecadien-1-ol, a sex pheromone of female moss, Bombyx mori, was synthesized stereospecifically. 2000 Elsevier Science Ltd.
- Uenishi, Jun'Ichi,Kawahama, Reiko,Izaki, Yoshiyuki,Yonemitsu, Osamu
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p. 3493 - 3500
(2007/10/03)
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- Alkene ozonolysis and the study of reactions of polyfunctional compounds: LXI. New synthetic route to bombycol, pheromone of mulberry silkworm
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Starting from a product of partial ozonolysis of 1,4-cyclohexadiene, methyl (E)-6-oxo-4-hexenoate, a new synthetic route was developed for (10E, 12Z)-hexadeca-10,12-dien-1-ol (bombycol), the main component of sex pheromone of mulberry silkworm (Bombix mori).
- Kukovinets,Kasradze,Chernukha,Odinokov,Dolidze,Galin,Spirikhin,Abdullin,Tolstikov
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p. 1156 - 1159
(2007/10/03)
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- Sex pheromone of the common sheep moth, Hemileuca eglanterina, from the San Gabriel Mountains of California
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The sex pheromone of Hemileuca eglanterina from the San Gabriel Mountains, California, was determined to be a combination of E10,Z12- hexadeca-10,12-dien-1-yl acetate, E10,Z12-hexadeca-10,12-dien-1-ol, and E10,Z12-hexadeca-10,12-dienal. Ratios of the compounds in extracts of female pheromone glands varied around a mean of 100:48:1.1 of the acetate, alcohol, and aldehyde, respectively. Field trials with synthetic compounds indicated that the optimum ratio of alcohol to aldehyde was 10:1 and that this ratio was more critical than the ratio of either compound to the acetate. A synthetic blend of 100:10:1 acetate-alcohol-aldehyde was effective at attracting male moths in the field. Additional compounds found in both extract and aeration samples failed to significantly increase trap catches of male moths, although some of these minor components elicited responses from male moth antennae in coupled gas chromatography-electroantennography studies.
- McElfresh, J. Steven,Millar, Jocelyn G.
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p. 687 - 709
(2007/10/03)
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- Stereospecific synthesis of (E,Z)- and (Z,Z)-hexadeca-10,12-dienal. Sex pheromone components of Diaphania hyalinata
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Isomeric (E,Z)- and (Z,Z)-hexadeca-10,12-dienal were prepared, stereospecifically, in 51% and 43% overall yields from dec-1-yne.
- Cabezas, Jorge A.,Oehlschlager, Allan C.
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p. 107 - 111
(2007/10/03)
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- INSECT PHEROMONES AND THEIR ANALOGUES XLVIII. A CONVENIENT SYNTHESIS OF THE 10E,12Z- AND 10E,12E-ISOMERS OF HEXADECADIEN-1-OL AND OF HEXADECA-10E,12Z-DIENAL - COMPONENTS OF THE SEX PHEROMONE OF THE SILKWORM MOTH
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The 10E,12Z- and 10E,12E-isomers of hexadecadien-1-ol and of hexadeca-10E,12Z-dienal - components of the sex pheromone of the silkworm moth Bombyx mori - have been synthesized from the readilly available octa-2E,7-dien-1-ol.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Ladenkova, I. M.,Sokol'skaya, O. V.,Muslukhov, R. R.,et al.
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p. 668 - 673
(2007/10/02)
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- HIGHLY STEREOSELECTIVE SYNTHESES OF CONJUGATED E,E- AND E,Z-DIENES, E-ENYNES AND E-1,2,3-BUTATRIENES VIA ALKENYLBORANE DERIVATIVES
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A highly selective and potentially general methodology for the synthesis of conjugated E,E- and E,Z-dienes, E-enynes, and E-1,2,3-butatrienes via hydroboration of alkynes is reported.The observed stereoselectivity was >98-99percent.
- Negishi, Ei-ichi,Yoshida, Takao,Abramovitch, Akiva,Lew, George,Williams, Robert M.
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p. 343 - 356
(2007/10/02)
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- A new synthesis of α,β-unsaturated aldehydes: Synthesis of traumatin and bombykol
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A novel conversion of an alkene to a higher homologue α,β-unsaturated aldehyde was achieved in three steps. The aldehydes were used for the synthesis of traumatin, a wound hormone and bombykol, the pheromone of bombyx mori.
- Dasaradhi,Neelakantan,Jagadishwar,Bhalerao
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p. 183 - 190
(2007/10/02)
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- AN EASY ROUTE TO INSECT PHEROMONES WITH A E-Z OR Z-E CONJUGATED DIENE STRUCTURE
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Insect pheromones having a conjugated diene system of E-Z or Z-E configuration can be prepared with high stereoselectivity, by means of addition reactions of Z-dialkenyl cuprates to phenylthioacetylene.The alkadienyl sulphides intermediates are then subjected to a cross-coupling reaction with Grignard reagents, in the presence of a Ni(II) complex as a catalysts, leading to the desired pheromones.
- Fiandanese, V.,Marchese, G.,Naso, F.,Ronzini, L.,Rotunno, D.
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p. 243 - 246
(2007/10/02)
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- A NEW APPROACH TO CONJUGATED DIENES SYNTHESIS OF THE PHEROMONES OF LOBESIA BOTRANA AND BOMBYX MORI
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Cis or trans epoxysilanes are regio and stereoselectively opened by Z-alkenyl cuprates, in the presence of BF3*OEt2, affording erythro or threo β-hydroxy silanes respectively.These are, in turn, transformed into E-Z conjugated dienes of high stereoisomeric purity by acidic or basic elimination.The method serves to synthetize the pheromones of Lobesia botrana and Bombyx mori.
- Alexakis, A.,Jachiet, D.
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p. 381 - 390
(2007/10/02)
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- Synthesis of (E,E)-10,12-hexadecadienal and (Z)-11-octadecenal
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Two economically important insect pheromones, viz. (E,E)-10,12-hexadecadien-1-al (1) and (Z)-11-octadecenal (2) of cotton pests have been synthesised from cheap and readily available materials utilising in situ alkylation of dianion of 4-pentyn-1-ol obtainable easily by lithium amide induced opening of tetrahydrofurfuryl chloride in liquid ammonia.
- Yadav, J. S.,Balakrishnan, Kamalam,Sivadasan, Latha
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p. 297 - 302
(2007/10/02)
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- A NEW STRATEGY FOR THE SYNTHESIS OF THE PHEROMONES of Lobesia botrana and Bombyx mori
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Opening of epoxysilanes by alkenyl cuprates reagents in the presence of BF3*Et2O afford β-hydroxysilanes which after basic or acidic treatment give the title pheromones.
- Alexakis, A.,Jachiet, D.
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p. 217 - 218
(2007/10/02)
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- STEREO- AND REGIOSPECIFIC SYNTHESES TO PROVIDE CONJUGATED (E, Z)- AND (Z,Z)-ALKANIDES, AND ARYLATED (Z)-ALKENES IN EXCELLENT YIELDS VIA THE PALLADIUM-CATALYZED CROSS COUPLING REACTIONS OF (Z)-1-ALKENYLBORONATES WITH 1-BROMOALKENES AND ARYL IODIDES
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Titled alkadienes are obtained in excellent yields stereo- and regiospecifically by cross-coupling between (Z)-1-alkenylboronates and (E)- or (Z)-1-bromoalkenes in the presence of a catalytic amount of Pd(PPh3)4 and sodium ethoxide.
- Miyaura, Norio,Satoh, Makoto,Suzuki, Akira
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p. 3745 - 3748
(2007/10/02)
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- Metamorphosis of Castor Oil to Insect Sex-pheromones and Useful Synthons
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The primary fragmentation products of Castor oil (1), namely, methyl undec-10-enoate (2) and sebacic acid (3) have been converted, using novel reactions and strategies into synthons of the type H-CC-(CH2)n-3-CH2OTHP (n=6=4; n=7=14; n=8=22; n=9=29).A surprisingly clean decarboxylative elimination of sebacic acid monoester gives methyl non-8-enoate (7), a synthon related to recefeiolide and a precursor to 4, the utility of which, has been illustrated with the synthesis of insect-pheromones of the species Grapholita molesta.Methyl dec-9-enoate (15) has been prepared by a novel and practical terminal ? to lower terminal ? degradation of 2.Compound 7 has been transformed via synthon 14 to the insect sex-pheromones of the species, Spodoptera frugiperda, Heliothis virescens and Paralobesia viteana in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxyundec-10-yne (22) readily prepared from 2, has been used to illustrate a new strategy in pheromone synthesis, namely, the use of coupling elements, leading to the preparation of bombykol in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxydodec-11-yne (29), already reported, has been transformed to vaccenic acid (30), the transposed ?-isomer of oleic acid, in good yields, thus demonstrating the use of acetylide synthons for the preparation of rare fatty acids also.
- Ranganathan, S.,Maniktala, Vibha,Kumar, Raaj,Singh, G. P.
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p. 1197 - 1207
(2007/10/02)
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- GENERAL METHODOLOGY FOR THE SYNTHESIS OF CONJUGATED DIENIC INSECT SEX PHEROMONES
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A general methodology for the synthesis of various type of dienic insect sex pheromones (Z-E, E-Z, Z-Z) is based on the carbocupration of acetylene by functionalised or non-functionalised lithium dialkyl cuprates, followed by the coupling of the resulting Z dialkenyl cuprates with functionalised or non-functionalised E or Z alkenyl iodides under Pd0 catalysis.The following compounds were efficiently synthesized with a high degree of stereoisomeric purity: (E-Z)7,9-dodecadien,-1-yl acetate 1 (Lobesia botrana), (E-Z)10,12-hexadecadien,-1-ol 2 (Bombyx mori), (Z-E)9,11-tetradecadien,-1-yl acetate 3 (Spodoptera littoralis), (Z-E)5,7 dodecadien-1-ol 4 (Malascoma disstria), (Z-Z)11, 13-Hexadecadien-1-al 5 (Amyelois transitella), (Z)9,11-dodecadien-1-yl acetate 6 (Diparopsis castanea) and (Z-Z)9,11-tridecadien-1-yl acetate 22 (a known "pseudo-pheromone").
- Gardette, M.,Jabri, A.,Alexakis, A.,Normant, J. F.
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p. 2741 - 2750
(2007/10/02)
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- NEW STEREOSPECIFIC SYNTHESES OF PHEROMONE BOMBYKOL AND ITS THREE GEOMETRICAL ISOMERS
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New stereospecific syntheses of the pheromone bombykol and its three geometrical isomers are achieved by palladium-catalyzed cross-coupling reaction between an appropriate alkenylborane and an alkenyl halide in the presence of a base.
- Miyaura, Norio,Suginome, Hiroshi,Suzuki, Akira
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p. 3271 - 3278
(2007/10/02)
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- NEW STEREOSPECIFIC SYNTHESES OF PHEROMONE BOMBYKOL AND ITS THREE GEOMETRICAL ISOMERS
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We describe stereospecific syntheses of pheromone, bombykol and the three geometrical isomers by means of the palladium-catalyzed cross-coupling between an appropriate alkenylborane and an alkenyl halide in the presence of a base.
- Miyaura, Norio,Suginome, Hiroshi,Suzuki, Akira
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p. 1527 - 1530
(2007/10/02)
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- SUBSTITUTION DES HALOGENO-1 ALCYNES-1 PAR LES DERIVES ORGANOMETALLIQUES DU CUIVRE. ACCES A UNE NOUVELLE CLASSE DE SYNTHONS: APPLICATION A LA SYNTHESE DU BOMBYKOL
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1-Bromo- and 1-iodo-1-alkynes are alkylated by organocopper(I) compounds.Alkenylcopper(I) derivatives undergo substitution with retention of configuration leading to conjugated and functional enynes, from which conjugated dienes can be obtained.
- Commercon, A.,Normant, J. F.,Villieras, J.
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p. 1215 - 1222
(2007/10/02)
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