- A simple synthesis of 4E,7Z-tridecadien-1-yl acetate, a component of the sex pheromone of the potato moth Phtorimaea operculella (Lepidoptera: Gelehiidae)
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A simple, five-step synthesis of the title compound was developed starting from commercially available 2,4-nonadienal. The overall yield of the pheromone is 29%, and the geometric purity of the Δ4 and Δ7 double bonds is ≥95%. The Z configuration of the Δ7 bond results from the 1,4-cis-hydrogenation of the intermediate 1,4,6-undecatrien-3-ol in the presence of an (arene)chromium tricarbonyl complex, while the E configuration of the Δ4 bond arises in the Claisen-Johnson rearrangement occuring in the reaction of 1,5Z-undecadien-3-ol with trimethyl orthoacetate.
- Vasil'ev,Serebryakov
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- Exo- and endohormones XXI 1: Stereoselective synthesis of the four isomers of the 4,7-tridecadien-1-yl acetate. (4E,7Z)-4,7-tridecadien-1-yl acetate, the sex pheromone of the leafminer moth Phylonorycter corylifoliella
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The synthesis of the four isomers of 4,7-tridecadien-1-yl acetate, based on a C5+C8 scheme is described. The coupling reaction took place between the Grignard reagent of pent-4-yn-1-oic acid and 1-bromo-2(Z/E)-octene. The four isomers were separated on SiO2-AgNO3 TLC plate and GS-MS. (4E,7Z)-4,7-Tridecadien-1-yl acetate is the sex pheromone of the spottet tentiform leafminer moth Phylonorycter corylifoliella.
- Ganscǎ, Lucia,Gocan, Alexandra,Oprean, Ioan,Maxim, Sanda,Budae, Iuliana
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p. 1243 - 1248
(2007/10/03)
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- Insect pheromones and their analogs LV. Synthesis of trideca-4E,7Z-dien-1-yl acetate - Component of the sex pheromone of Phthorimaea opercucella
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Starting from propargyl alcohol and using the thermal Claisen rearrangement at the stage of constructing the (E)-double bond, we have synthesized trideca-4E, 7Z-dien-1-yl acetate - a component of the sex pheromone of the potato moth Phthorimaea opercucella (Zeller).
- Odinokov,Vakhidov,Shakhmaev,Zorin
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p. 350 - 352
(2007/10/03)
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- Stereoselective Synthesis of 1,4-Dienes. Application to the Preparation of Insect Pheromones (3Z,6Z)-Dodeca-3,6-dien-1-ol and (4E,7Z)-Trideca-4,7-dienyl Acetate
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Stereoselective synthesis of Z,E- and Z,Z-1,4-dienes has been achieved by the cross-coupling of allylic substrates with vinyl organometallic reagents.Key to this strategy was the development of a method for regiospecific incorporation of a tri-n-butylstannyl group in the γ-position of the allylic cross-coupling partner.The steric bulk of this moiety ensures the stereochemical integrity of the allylic double bond throughout the coupling sequence and is easily replaced by hydrogen in the coupled product.This strategy has been applied to the synthesis of the termite trail marker pheromone 22 and the leafminer moth sex pheromone 28.
- Hutzinger, Michael W.,Oehlschlager, Allan C.
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p. 4595 - 4601
(2007/10/02)
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- EXO- AND ENDOHORMONES, XVI SYNTHESIS OF (4E, 7Z)-4,7-TRIDECADIEN 1-YL ACETATE, THE SEX PHEROMONE FOR THE LEAFMINER LITHOCOLLETIS CORYLIFOLIELLA
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The synthesis of the sex pheromone of the leafminer moth, Lithocolletis corylifoliella, (4E, 7Z)-4,7-tridecadien-1-yl acetate, was based on a C5+C8 scheme.The coupling reaction took place between the Grignard reagent of 4-pentin-1-1-oic acid and 1-bromo-2Z-octene.Propargylic alcohol was used as a starting material in order to obtain the two synthons.
- Gocan, Alexandra,Gansca, Lucia,Oprean, Ioan
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p. 253 - 258
(2007/10/03)
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- ALKYLATION OF ACETYLCYCLOPROPANE CYCLOHEXYLIMINE BY ETHYLENE OXIDE DERIVATIVES AS A KEY STEP IN THE SYNTHESIS OF SOME INSECT ACETOGENIN PHEROMONES
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The interaction of Li derivatives of acetylcyclopropane cyclohexylimine with ethylene, propylene, and isoprene oxides leads efficiently to the corresponding γ-cyclopropylketols.The cyclopropylcarbinol corresponding to the first of them is smoothly converted under the action of the couple Me3SiBr/ZnBr2 to a linear E-C7-homoallyl bromide, which is then used in the stereocontrolled synthesis of tridec-4E-enyl and trideca-4E,7Z-dienyl acetates - components of the sex pheromones of some Lepidoptera species.Keywords: acetylcyclopropane, insect acetogenin pheromones, homoallyl rearrangement, Julia olefination, olefin oxides.
- Ivanova, N. M.,Cheskis, B. E.,Moiseenkov, A. M.,Nefedov, O. M.
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p. 1853 - 1857
(2007/10/02)
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- Acetylcyclopropane as a Five-Carbon Building Block in the Synthesis of some Acetogenin Insect Pheromones
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Interaction of deprotonated acetylcyclopropane cyclohexylimine with several aliphatic alkyl halides, epoxides, and aldehydes efficiently gave the corresponding cyclopropyl ketones.Some of the respectible alcohols were rearranged in a highly stereoselective manner under the action of trimethylsilyl bromide in the presence of zinc bromide into the corresponding linear (E)-homoallyl bromides.The latter were used, in turn, as key intermediates in concise syntheses of thirteen terminally functionalized straight-chain oligoolefins which are known to constitute acetogenin pheromonal components for more than 65 species of lepidopteran insects.
- Moiseenkov, Alexander M.,Czeskis, Boris A.,Ivanova, Natalya M.,Nefedov, Oleg M.
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p. 2639 - 2649
(2007/10/02)
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- Organoaluiminum-promoted claisen rearrangement of allyl vinyl ethers
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Unprecedentad stereochemical control has achieved in the Claisen of allyl vinyl of type 4 with certain bulky organoaluminum Thus, methylaluminum bis(4-bromo-2,6-di-tert-butylphenoxide) (reagent A) can be utilized for obtaining the (Z) isomer, (Z)-6, whereas the (E) isomer, (E)-6 was produced with methylaluminum bis(2,6-diphenylphenoxide) (reagent B). This organoaluminum-promoted Claisen rearrangement proceeds under very mild conditions with very good E and Z selectlvities. On the basis of the Claisen rearrangement of optically active substrate 7 with reagent A, the Z selectivity would be interpreted by the intervention of the chairlike transition-state conformation with the isobutyl substituent axial. The present organoalunminum-promoted Claisen rearrangement has successfully applied to the synthesis of (4E,7Z)-4,7-tridecadienyl acetate (15), a component of the sex of tuberworm moth, in stereoselective fashion. Furthermore, the Claisen rearrangement of bisallyl vinyi ether16 with reagent A or B has been found to involve the more substituted allylic system to furnish dienal 18 preferentially, not obtainable in the ordinary thermal rearrangement. This chemistry been further extended to the ionic rearrangement of dienyl vinyl ether 28 by using reagent A in a polar solvent the previously unknown, remote transfer of the vinyloxy moiety by [3,5]-sigmatropic rearrangement via ionic intermediate 29 has observed.
- Nonshita, Katsumasa,Banno, Hiroshi,Maruoka, Keiji,Yamamoto, Hishashi
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p. 316 - 322
(2007/10/02)
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Coupling reactions of lithium compounds, (Z)-carbonyl olefination of phosphonium ylides and 'crossed' Wittig olefination of bisylides are the key reaction steps in the synthesis principle for nonconjugated, bisolefinic Lepidoptera pheromones and structural analogs. Double unsaturated (E,Z)- and (E,E)-1-vinyl halides are converted into the corresponding (E,Z)- and (E,E)-1-vinyl lithium compounds and coupled selectively to (E,Z)- and (E,E)-alkadienols, alkadienals and alkadienyl acetates with different carbon chain length, geometry and relative positions of double bonds. 'Crossed' Wittig reactions of 1,ω-alkylidene bisylides with two different alkanals gives rise to the formation of corresponding (Z,Z)-dienic sex attractants and derivatives. A monounsaturated (E)-1-vinyl iodide is the synthon for the preparation of an (E)-alkenyl bromide which is converted to an (E)-alkenyl phosphonium salt and (Z)-selectively olefinated to (Z,E)-isomers of moth sex pheromones.
- Bestmann,Zeibig,Vostrowsky
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p. 1039 - 1047
(2007/10/02)
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- SYNTHETIC INVESTIGATIONS IN THE FIELD OF INSECT ATTRACTANTS (SEX ATTRACTANTS). II. SYNTHESIS OF FOUR ISOMERS OF 4,7-TRIDECADIENYL ACETATE AND (E,Z,Z)-4,7,10-TRIDECATRIENYL ACETATE
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A common approach was developed to the synthesis of (E,Z)-4,7-tridecadienyl and (E,Z,Z)-4,7,10-tridecatrienyl acetates, which are the main components of the sex pheromone of the female potato moth Phtorimaea operculella, on the basis of 4-pentyn-1-ol and allyl halides.The Z,Z, Z,E, and E,E isomers of 4,7-tridecadienyl acetate were also obtained by the method.
- Ishchenko, R. I.,Kovalev, B. G.
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p. 258 - 262
(2007/10/02)
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- SILICON-DIRECTED BECKMANN FRAGMENTATION
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The selective fragmentation reactions of β-trimethylsilylketoximes have been proved to proceed effectively with acid catalysts giving the corresponding nitriles.Cyclic silylketoximes gave unsaturated nitriles.The fragmentation in the Beckmann rearrangement is completely controlled and directed by a trimethylsilyl group to lead the regio- and stereo-specific formation of the double bond.The catalytic fragmentation proceeds with the combination of trimethylsilyl ketoxime acetates and trimethylsilyl trifluoromethanesulfonate giving nitriles in high yields.Excellent stereospecificity of the fragmentation based on the stereochemical outcome was discussed.Simple stereo-controlled synthetic approach to some insect pheromones is also described.
- Nishiyama, Hisao,Sakuta, Koji,Osaka, Noriyuki,Arai, Hiroyuki,Matsumoto, Makoto,Itoh, Kenji
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p. 2413 - 2426
(2007/10/02)
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- Synthesis of Pheromones of Potato Tuberworm Moth, Phthorimaea opericulella (Zeller)
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The alcohol (3) having highly flexible dual functionality (terminal acetylene and a terminal double bond), has been utilised for the synthesis of (n,n+3) alkadienes.The simplicity of this procedure has been illustrated by the synthesis of potato tuberworm moth pheromones, PTM-1 (1a) and PTM-2 (1b).
- Chattopadhyay, A.,Mamdapur, V. R.,Chadha, M. S.
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p. 187 - 188
(2007/10/02)
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- Synthesis of (4E,7Z)-4,7-Tridecadienyl Acetate and (4E,7Z,10Z)-4,7,10-Tridecatrienyl Acetate - The Sex Pheromones of Potato Tuberworm Moth
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(4E,7Z)-4,7-Tridecadienyl acetate (1) and (4E,7Z,10Z)-4,7,10-tridecatrienyl acetate (2), the sex pheromones of potato tuberworm moth have been synthesized from a common intermediate 1-hexen-5-yn-3-ol (3) employing Claisen rearrangement as a key step to generate the trans-double bond.
- Yadav, J. S.,Kulkarni, A. D.,Reddy, P. Satyanarayana
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p. 1220 - 1223
(2007/10/02)
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- ALLYLATION OF GRIGNARD REAGENTS: ITS APPLICATION FOR THE SYNTHESIS OF (4E,7Z)-4,7-TRIDECADIENYL ACETATE, A SEX PHEROMONE OF POTATO TUBERWORM MOTH
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Alkylmagnesium halides have been found to react with (Z)-4-benzyloxy-1-chloro-2-butene in presence of HMPA to produce a rearranged product 3-alkyl-4-benzyloxy-1-butene, while the absence of HMPA a normal product (Z)-1-alkyl-4-benzyloxy-2-butene resulted as the predominant product.Latter product has been utilized for the synthesis of (4E,7Z)-4,7-tridecadienyl acetate, a sex pheromone of potato tuberworm moth.
- Yadav, J. S.,Reddy, P. Satyanarayana
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p. 1119 - 1132
(2007/10/02)
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- Synthesis of (4E,7Z)-4,7-tridecadien-1-yl Acetate
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(Z)-5-Undecen-2-yn-1-ol (II) on reduction with LAH produces (2E,5Z)-2,5-undecadien-1-ol (III) which gives the bromide (IV) on treatment with PBr3/ pyridine.The diester (V) resulting from alkylation of diethylmalonate with IV on decarbethoxylation generates ethyl (4E,7Z)-4,7-tridecadienoate (VI) which on reduction with lithium aluminium monoethoxy hydride affords (4E,7Z)-4,7-tridecadien-1-ol (VII).The dienol (VII) converts into the title compound (I) on reaction with acetic anhydride/ pyridine.
- Vig, O. P.,Sharma, M. L.,Kumari, Sarla,Rani, Veena
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p. 675 - 676
(2007/10/02)
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- NEW STEREOCONTROLLED APPROACH TO SOME INSECT PHEROMONES VIA SILICON-DIRECTED BECKMANN FRAGMENTATION
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The major components of sex pheromones of potato tuberworm moth and Douglas fir tussock moth have been synthesized via the regio- and stereo-controlled Beckmann fragmentation assisted by trimethylsilyl group.
- Nishiyama, Hisao,Sakuta, Koji,Itoh, Kenji
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p. 223 - 226
(2007/10/02)
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- SIMPLE METHODS FOR, THE SYNTHESIS OF (E)-4- AND (E)-5-ALKENOIC ACIDS BY THE SN2' TYPE REACTIONS OF γ-VINYL-γ-BUTYROLACTONE AND δ-VINYL-δ-VALEROLACTONE WITH ORGANOCOPPER REAGENTS
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γ-Vinyl-γ-butyrolactone and δ-vinyl-δ-valerolactone react regio- and stereoselectively with Grignard reagents in the presence of a copper(I) catalyst or with diorganocuprates to afford (E)-4- and (E)-5-alkenoic acids, respectively, in high yields.Synthetic utility of the former reaction is demonstrated in the simple synthesis of (4E,7Z)-4,7-tridecadienyl acetate.
- Fujisawa, Tamotsu,Sato, Toshio,Kawashima, Masatoshi,Naruse, Kouichi,Tamai, Kouichi
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p. 3583 - 3586
(2007/10/02)
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