- Continuous Flow Z-Stereoselective Olefin Metathesis: Development and Applications in the Synthesis of Pheromones and Macrocyclic Odorant Molecules**
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The first continuous flow Z-selective olefin metathesis process is reported. Key to realizing this process was the adequate choice of stereoselective catalysts combined with the design of an appropriate continuous reactor setup. The designed continuous process permits various self-, cross- and macro-ring-closing-metathesis reactions, delivering products in high selectivity and short residence times. This technique is exemplified by direct application to the preparation of a range of pheromones and macrocyclic odorant molecules and culminates in a telescoped Z-selective cross-metathesis/ Dieckmann cyclisation sequence to access (Z)-Civetone, incorporating a serial array of continually stirred tank reactors.
- Browne, Duncan L.,Colombel-Rouen, Sophie,Crévisy, Christophe,Curbet, Idriss,Mauduit, Marc,McBride, Tom,Morvan, Jennifer,Roisnel, Thierry
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supporting information
p. 19685 - 19690
(2021/08/06)
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- Stereoselective Chromium-Catalyzed Semi-Hydrogenation of Alkynes
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Chromium complexes have found very little applications as hydrogenation catalysts. Here, we report a Cr-catalyzed semi-hydrogenation of internal alkynes to the corresponding Z-alkenes with good stereocontrol (up to 99/1 for dialkyl alkynes). The catalyst comprises the commercial reagents chromium(III) acetylacetonate, Cr(acac)3, and diisobutylaluminium hydride, DIBAL?H, in THF. The semi-hydrogenation operates at mild conditions (1-5 bar H2, 30 °C).
- Gregori, Bernhard J.,Nowakowski, Michal,Schoch, Anke,P?llath, Simon,Zweck, Josef,Bauer, Matthias,Jacobi von Wangelin, Axel
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p. 5359 - 5363
(2020/09/03)
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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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- 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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- Production of pheromones and fragrances from substituted and unsubstituted 1-alken-3yl alkylates
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Compounds of the formula (I) wherein R2 is a branched or unbranched, saturated or ethylenically mono or di unsaturated aliphatic radical, Z is —CH2OH, —CH2OAc or —CHO, m is a whole positive integer of one or more, and Ac is an acetyl group are synthesized by a process wherein a 1-alken-3-yl alkylate, is reacted with a halo alkanol Grignard reagent.
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Page/Page column 5
(2010/05/13)
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- Preparative synthesis of (Z)-5-decenyl acetate
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A procedure was developed for preparative synthesis of (Z)-5-decenyl acetate, the sex hormone of Agrotis Segetum.
- Chobanyan
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p. 2036 - 2037
(2007/10/03)
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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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- 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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- 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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- 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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p. 497 - 499
(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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- 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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- 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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