- INSECT PHEROMONES AND THEIR ANALOGUES XXXI. SYNTHESIS OF DEC-5Z-EN-1-YL ACETATE AND HENEICOS-6Z-EN-11-ONE FROM A FUNCTIONALLY DIFFERENTIATED PRODUCT OF THE OZONOLYSIS OF CYCLOPENTENE
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Dec-5Z-en-1-yl acetate and heneicos-6Z-en-11-one - pheromones of insects of the genera Agrotis and Orgyia, respectively - have been synthesized from a product of the functionally differentiated ozonolysis of cyclopentene.
- Odinokov, V. N.,Akhmetova, V. R.,Khasanov, Kh. D.,Abduvakhabov, A. A.,Tolstikov, O. A.
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- PHEROMONES, 71. IDENTIFICATION AND SYNTHESIS OF FEMALE SEX PHEROMONE OF ERI-SILKWORM, Samia cynthia ricini (LEPIDOPTERA: SATURNIIDAE)
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(4E,6E,11Z)-4,6,11-Hexadecatrienal and (4E,6E,11Z)-4,6,11-hexadecatrienyl acetate were identified as the major components of the sex pheromone of the eri-silkworm, Samia cynthia ricini, females.
- Bestmann, Hans Juergen,Attygalle, Athula B.,Schwarz, Juergen,Garbe, Wolfgang,Vostrowsky, Otto,Tomida, Ichiro
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- An Amine-Assisted Ionic Monohydride Mechanism Enables Selective Alkyne cis-Semihydrogenation with Ethanol: From Elementary Steps to Catalysis
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The selective synthesis of Z-alkenes in alkyne semihydrogenation relies on the reactivity difference of the catalysts toward the starting materials and the products. Here we report Z-selective semihydrogenation of alkynes with ethanol via a coordination-induced ionic monohydride mechanism. The EtOH-coordination-driven Cl- dissociation in a pincer Ir(III) hydridochloride complex (NCP)IrHCl (1) forms a cationic monohydride, [(NCP)IrH(EtOH)]+Cl-, that reacts selectively with alkynes over the corresponding Z-alkenes, thereby overcoming competing thermodynamically dominant alkene Z-E isomerization and overreduction. The challenge for establishing a catalytic cycle, however, lies in the alcoholysis step; the reaction of the alkyne insertion product (NCP)IrCl(vinyl) with EtOH does occur, but very slowly. Surprisingly, the alcoholysis does not proceed via direct protonolysis of the Ir-C(vinyl) bond. Instead, mechanistic data are consistent with an anion-involved alcoholysis pathway involving ionization of (NCP)IrCl(vinyl) via EtOH-for-Cl substitution and reversible protonation of Cl- ion with an Ir(III)-bound EtOH, followed by β-H elimination of the ethoxy ligand and C(vinyl)-H reductive elimination. The use of an amine is key to the monohydride mechanism by promoting the alcoholysis. The 1-amine-EtOH catalytic system exhibits an unprecedented level of substrate scope, generality, and compatibility, as demonstrated by Z-selective reduction of all alkyne classes, including challenging enynes and complex polyfunctionalized molecules. Comparison with a cationic monohydride complex bearing a noncoordinating BArF- ion elucidates the beneficial role of the Cl- ion in controlling the stereoselectivity, and comparison between 1-amine-EtOH and 1-NaOtBu-EtOH underscores the fact that this base variable, albeit in catalytic amounts, leads to different mechanisms and consequently different stereoselectivity.
- Huang, Zhidao,Wang, Yulei,Leng, Xuebing,Huang, Zheng
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supporting information
p. 4824 - 4836
(2021/04/07)
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- Synthesis and Immobilization of Metal Nanoparticles Using Photoactive Polymer-Decorated Zeolite L Crystals and Their Application in Catalysis
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A facile route to generate Au and Pd nanoparticles (NPs) on zeolite L crystals decorated with photoactive polymer brushes is described. The polymers used in this approach serve a dual role: Upon irradiation with UV light, they release highly reducing ketyl radicals in a Norrish-Type-I reaction. These radicals serve as one electron donors to reduce metal salts to the corresponding metal NPs. At the same time the polymer shell stabilizes the in situ generated metal NPs. It is shown that the zeolite-polymer-NP composites can be used as recyclable catalysts for the oxidation of benzylic alcohols to aldehydes and the stereoselective semihydrogenation of alkynes to Z-alkenes. The polymer shell in these hybrid catalysts protects the NPs from aggregation and also alters their catalytic properties. (Figure presented.).
- Wissing, Maren,Niehues, Maximilian,Ravoo, Bart Jan,Studer, Armido
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supporting information
p. 2245 - 2253
(2020/05/05)
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- Stereoselective Alkyne Hydrogenation by using a Simple Iron Catalyst
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The stereoselective hydrogenation of alkynes constitutes one of the key approaches for the construction of stereodefined alkenes. The majority of conventional methods utilize noble and toxic metal catalysts. This study concerns a simple catalyst comprised of the commercial chemicals iron(II) acetylacetonate and diisobutylaluminum hydride, which enables the Z-selective semihydrogenation of alkynes under near ambient conditions (1–3 bar H2, 30 °C, 5 mol % [Fe]). Neither an elaborate catalyst preparation nor addition of ligands is required. Mechanistic studies (kinetic poisoning, X-ray absorption spectroscopy, TEM) strongly indicate the operation of small iron clusters and particle catalysts.
- Gregori, Bernhard J.,Schwarzhuber, Felix,P?llath, Simon,Zweck, Josef,Fritsch, Lorena,Schoch, Roland,Bauer, Matthias,Jacobi von Wangelin, Axel
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p. 3864 - 3870
(2019/07/31)
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- Pyrrolidines and Piperidines by Ligand-Enabled Aza-Heck Cyclizations and Cascades of N-(Pentafluorobenzoyloxy)carbamates
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Ligand-enabled aza-Heck cyclizations and cascades of N-(pentafluorobenzoyloxy)carbamates are described. These studies encompass the first examples of efficient non-biased 6-exo aza-Heck cyclizations. The methodology provides direct and flexible access to carbamate protected pyrrolidines and piperidines.
- Hazelden, Ian R.,Carmona, Rafaela C.,Langer, Thomas,Pringle, Paul G.,Bower, John F.
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supporting information
p. 5124 - 5128
(2018/03/26)
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- Facile Light-Mediated Preparation of Small Polymer-Coated Palladium-Nanoparticles and Their Application as Catalysts for Alkyne Semi-Hydrogenation
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A facile light-mediated preparation of small palladium nanoparticles (PdNPs) with a diameter of 1.3 nm and low dispersity by using low-priced and readily prepared photoactive polymers is presented. These polymers act as reagents for the photochemical reduction of Pd ions and they are also stabilizers for the PdNPs generated in situ. The PdNP–polymer hybrid materials prepared by this reliable approach are efficient hydrogenation catalysts that show high activity and Z-selectivity in the semi-hydrogenation of alkynes. These PdNP–catalyst hybrid materials can be readily recycled and reused up to five times.
- M?sing, Florian,Wang, Xi,Nüsse, Harald,Klingauf, Jürgen,Studer, Armido
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supporting information
p. 6014 - 6018
(2017/05/05)
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- Light Mediated Preparation of Palladium Nanoparticles as Catalysts for Alkyne cis-Semihydrogenation
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A bisacylphosphine oxide photoinitiator was used for the light mediated preparation of palladium nanoparticles (PdNPs) with a small diameter of 2.8 nm. All starting materials are commercially available, and PdNP synthesis is experimentally very easy to conduct. The PdNP-hybrid material was applied as catalyst for the semihydrogenation of various internal alkynes to provide the corresponding alkenes in excellent yields (up to 99%) and Z-selectivities (Z/E ratios up to 99/1).
- M?sing, Florian,Nüsse, Harald,Klingauf, Jürgen,Studer, Armido
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supporting information
p. 2658 - 2661
(2017/05/24)
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- Synthesis of heneicos-6(Z)-en-11-one, dec-5(Z)-en-l-yl acetate, dec-5(Z)-En-1-y1-3-methylbutanoate (insect sex pheromones)
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Synthesis of heneicos-6(Z)-en-11-one 1, dec-5(Z)-en-l-yl acetate 2, dec-5(Z)-en-l-yl-3-methylbutanoate 3 has been accomplished by utilizing sodium acetoxyborohydride generated in situ from sodium borohydride and acetic acid as the key step for selective hydroboration-iodination/oxidation.
- Jindal, Rani,Devi, Aarti,Kad, Goverdhan L.,Singh, Jasvinder
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experimental part
p. 495 - 499
(2010/10/20)
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- A selective Ru-catalyzed semireduction of alkynes to Z olefins under transfer-hydrogenation conditions
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By using a readily available, air- and moisture-stable dihydrido-Ru complex, a variety of Z olefins are accessible under transfer-hydrogenation conditions with formic acid as the hydrogen source in excellent yields and Z/E selectivities. A discerning transformation: Z-Configured C=C bonds are stereoselectively formed from alkynes in the presence of a Ru catalyst with formic acid as the sole H2 source at room temperature (see scheme). A variety of functional groups are compatible with this novel procedure. Operational simplicity and the lack of overreduction products are characteristics for this unprecedented process.
- Belger, Christian,Neisius, N. Matthias,Plietker, Bernd
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supporting information; experimental part
p. 12214 - 12220
(2011/03/17)
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- Synthesis of (Z)-5-decenol and (Z)-5-decenyl acetate, components of the sex pheromones of a variety of lepidoptera
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Two simple Wittig procedures for the synthesis of (Z)-5-decenol and (Z)-5-decenyl acetate based on the monoacetylation or monobromination of 1,5-pentanediol were followed.
- Tortajada, Amparo,Mestres, Ramon,Iglesias-Arteaga, Martin A.
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p. 1809 - 1814
(2007/10/03)
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- Suzuki-Miyaura cross-coupling of lithium n-alkylborates
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The palladium-catalyzed cross-coupling of lithium n-alkylborates, generated in situ via addition of sec-butyl lithium to boronate esters, proceeds in moderate to good yields with a wide variety of electrophiles.
- Zou, Gang,Falck
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p. 5817 - 5819
(2007/10/03)
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- New synthesis of (Z)-5- and (Z)-7-monoene components of insect sex pheromones of the Lepidoptera order
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A new procedure was developed for the synthesis of (Z)-5- and (Z)-7-monoene components of sex pheromones of Lepidoptera insects based on cometathesis of readily accessible cycloocta-1,5-diene and ethylene.
- Bykov,Butenko,Egupova,Finkelshtein
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p. 1301 - 1304
(2007/10/03)
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- Synthesis of sub-units of marine polycyclic ethers by ring-closing metathesis and hydroboration of enol ethers
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A novel syntheses of Z-5-dezenol, Z-5-decenyl acetate, Z-7-dodecenol, Z- 7-dodecenyl acetate, Z-9-tricosene, Z-7,8-epoxy-methyloctadecane which are sex pheromone components of Lepidoptera and Diptera orders, have been realized via stereoselective cometathesis of 1,5-cyclooctadiene with ethylene in the presence of MoCls/SiO2-SnMe4 as a key reaction. The male cometathesis product, 1,Z-5,9-decatriene, has been converted into pheromone components monocloned above by regioselective partial hydroboration or hydrozirconation with help of 9-BBN and Cp2ZrHCl, correspondingly. The protonolysis of the obtained zirconosene derivative gave 1,Z-5-decadiene. Hydroboration-oxidation or hydroboration-C2-homologation of the latter but to Z-5- or Z-7 monoene pheromone components. Hydroboration-iodination of terminal double bond in 1,Z-5,9-decatriene, and further cross-coupling of the obtained iodine derivative with convenient lithium cuprates resulted in Z-9- tricosene, the main sex pheromone component of House Fly (Musca Domestica), or in 2-methyl-Z-7-octadecene, the presence of Gypsy Moth (Lymantria Dispar) sex attractant.
- Bykov, Victor I.,Butenko, Tamara A.,Petrova, Elena B.,Finkelshtein, Eugene Sh.
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p. 8249 - 8252
(2007/10/03)
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- Chemistry of natural compounds and bioorganic chemistry a convergent synthesis of octadeca-2E,13Z-dienyl acetate, a pheromone component of Synanthedon tipuliformis C
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A convergent synthesis of octadeca-2E,13Z-dienyl acetate, a pheromone component of Synanthedon tipuliformis C., has been developed. The synthesis is based on cross-coupling of 8-iodooct-2E-en-1-ol THP ether with dec-57-enyl bromide catalyzed by CuBr.
- Ishmuratov,Yakovleva,Kharisov,Kunafina,Gorobets,Kuchin,Tolstikov
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p. 1465 - 1467
(2007/10/03)
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- Reactions of α-epoxysilanes with organocopper reagents. A stereoselective route to alkenes
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Reactions of α-epoxysilanes with cuprate reagents can be controlled to give β-silyl alcohols as major products. An oxidation, Grignard addition, and elimination sequence then provides alkenes with up to 98% de.
- Chauret, Denise C.,Chong, J. Michael
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p. 3695 - 3698
(2007/10/02)
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- Cyclic ethers as educts for the synthesis of lepidoptra pheromones
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ω-Iodo(trialkylsiloxy)alkanes 2 prepared by ring opening of cyclic ethers with iodotrimethylsilane, are useful starting materials for the synthesis of pheromone components. Reaction with triphenylphosphine to give the corresponding Wittig reagent and subsequent coupling with lithium (Z)-dihex-1-enylcuprate gives (Z)-alken-1-ols 5 and 7, after deprotection, in good yields. The direct coupling of 2 with alkynes failed because of competition reactions, however, the more stable ω-iodo-1-(tert-butyldimethylsiloxy)alkanes were able to undergo C,C-coupling with alkynes. The thus formed 1-(tert-butyldimethylsiloxy)-5-decyne (13c) was hydrogenated and deprotected to give (E)-5-decen-1-ol (15c).
- Poleschner,Heydenreich,Martin
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p. 1231 - 1235
(2007/10/02)
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- Triply Convergent, Stereospecific Alkene Formation via Peterson Olefination
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α-Iodo silanes 8 were prepared from α-hydroxy silanes and after halogen/metal exchange and treatment with copper(I)bromide-dimethyl sulfide were coupled with acid chlorides to yield α-silyl ketones 2.Cram controlled addition with a variety of nucleophiles followed by treatment with acid or base led to either the (E)- or (Z)-alkene in good overall yields from the iodide (47-67percent) and with excellent stereoselectivities (>95/95/5 isomeric purity.
- Barrett, Anthony G. M.,Flygare, John A.
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p. 638 - 642
(2007/10/02)
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- EFFICIENT SYNTHESIS OF 3E,13Z-OCTADECADIENOL, ITS ACETATE, 4E,6E,11Z-HECADECATRIENAL, AND 4E,6E,11Z-HEXADECATRIENYL ACETATE, SEX PHEROMONES OF SOME LEPIDOPTERAN SPECIES
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The title linear acetogenins have been synthesized by a strategy of joining acetylcyclopropane to 8Z-tridecenol or 5Z-decenol prepared after Julia, leading to the corresponding secondary cyclopropylcarbinols.The ZnBr2/Me3SiBr-initiated homoallylic rearrangement of the latter assures at a key step the stereospecific construction of transoid fragments of the target molecules.
- Ivanova, N. M.,Cheskis, B. A.,Moiseenkov, A. M.,Nefedov, O. M.
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p. 2196 - 2204
(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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- SYNTHESES OF SOME cis-MONO-OLEFINIC INSECT SEX PHEROMONES
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A convenient synthesis of cis mono-olefinic pheromone components I, II, and III has been achieved starting from (Z)-5-(2-tetrahydropyranyloxy)-pent-2-yn-1-ol (V) and (Z)-7-(2-tetrahydropyranyloxy)-hept-2-yn-1-ol (IV), both of which have been obtained from a common intermediate, viz. the dianion of prop-2-yn-1-ol.
- Sharma, Madan L.,Gupta, Rashmi,Verma, Sadhana
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p. 1744 - 1748
(2007/10/02)
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- Ozonolysis of alkenes and the reactions of polyfuctional compounds. XXXIX. Partial ozonolysis of (Z,Z)-1,6-cyclodecadiene in the synthesis of the pheromones of insects of the order lepidoptera
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A stereospecific synthesis of 5Z-decen-1-yl and 9Z-tetradecen-1-yl acetates, which are components of the sex pheromones of winter (Agrotis segetum) and pine (Panolis flammea) cutwords respectively, was realized by partial ozonolysis of (Z,Z)-1,6-cyclodecadiene.
- Odinakov, V. N.,Ishmuratov, G. Yu.,Galeeva, R. I.,Sokol'skaya, O. V.,Sagitdinova, Kh. F.,Tolstikov, G. A.
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- SYNTHESIS OF PHEROMONES, IV. CHEMISTRY OF THE WITTIG REACTION, I. EFFECTS OF REACTION CONDITIONS ON THE STEREOSELECTIVITY AND YIELD OF THE WITTIG REACTION
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The reactions of nonstabilized triphenylphosphorus ylides with aldehydes have been studied in detail.The stereochemistry and yields of the alkene products are highly dependent upon base used for the generation of the ylide, the solvent and reaction temperature.The synthesis of sex pheromone components by Wittig reaction are also described.
- Vinczer, Peter,Juvancz, Zoltan,Novak, Lajos,Szantay, Csaba
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p. 797 - 820
(2007/10/02)
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- Applications of the Stereochemically-Controlled Horner-Wittig Reaction: Synthesis of Feniculin, (E)-Non-6-en-1-ol, a Pheromone of the Mediterranean Fruit Fly, (E)- and (Z)-Dec-5-en-1-ol, Tri-substituted Alkenes, and (Z)-α-Bisabolene
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Stereoselective reduction of the appropriate α-diphenylphosphinoyl ketone or addition of the lithium derivative of an alkyl diphenylphospine oxide to an aldehyde or a ketone gives Horner-Wittig intermediates and hence the title compounds.
- Buss, Antony D.,Greeves, Nicholas,Mason, Ralph,Warren, Stuart
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p. 2569 - 2578
(2007/10/02)
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- INSECT PHEROMONES AND THEIR ANALOGS. XII. SYNTHESIS OF THE ISOMERIC DEC-5-ENYL ACETATES - THE SEX PHEROMONES OF Anarsia lineatella AND Agrotis segetum
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A new route for the synthesis of dec-5E- and -5Z-enyl acetates - the sex pheromones of the peach-tree borer and of the turnip moth - is proposed which is based on the two-stage hydroxyethylation of hex-1-yne using 2-chloroethyl vinyl ethers and ethylene oxide.
- Odinokov, V. N.,Balezina, G. G.,Ishmuratov, G. Yu.,Vakhitov, R. Sh.,Tolstikov, G. A.
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p. 369 - 371
(2007/10/02)
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- STEREOCHEMICALLY CONTROLLED SYNTHESIS OF UNSATURATED ACIDS VIA DIPHENYLPHOSPHINOYL(Ph2PO)-KETOACIDS
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Acylation of phosphine oxide anions with derivatives of cyclic anhydrides or oxidative cleavage of cyclic allyl phosphine oxides gives Ph2PO-ketoacids: reduction, separation of diastereoisomers, and completion of the Horner-Wittig reaction gives single isomers (E or Z) of unsaturated acids.
- Levin, Daniel,Warren, Stuart
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p. 505 - 508
(2007/10/02)
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- SYNTHESIS OF SINGLE ISOMERS (E OR Z) OF UNSATURATED ALCOHOLS BY THE HORNER-WITTIG REACTION
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Single isomers (E or Z) of homoallylic and higher alcohols can be synthesised from ω-hydroxyalkyldiphenylphosphine oxides and aldehydes, or from alkyldiphenylphosphine oxides and lactones
- Buss, Antony D,Greeves, Nicholas,Levin, Daniel,Wallace, Paul,Warren, Stuart
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p. 357 - 360
(2007/10/02)
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