- Synthesis Method of Cyclopropane or Cyclopentene Derivatives via Fe-catalyzed Cationic Radical Cycloaddition Reaction
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In this disclosure Fe (III) complex is used as an electron oxidizing agent to oxidize an electron - rich alkene compound to form a radical cation intermediate, and then a cyclopropane compound or 3 5-membered ring compound is synthesized by inducing a cycloaddition reaction with the diazo compound.
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Paragraph 0080-0081; 0101-0102
(2021/11/02)
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- Asymmetric cyclopropanation method of copper-catalyzed olefin and application of asymmetric cyclopropanation method
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The invention discloses an asymmetric cyclopropanation method of copper-catalyzed olefin and application thereof. The copper catalyst adopted by the method is generated in situ from a metal copper precursor and a chiral P, N, N-ligand in a reaction medium. The method has the characteristics of cheap catalyst, simple ligand preparation, high activity, high selectivity, mild reaction conditions, simple operation and the like, can realize continuous operation, and is suitable for large-scale industrial production. The method is also suitable for asymmetric synthesis of chiral first chrysanthemic acid which is an important intermediate of pyrethroid pesticides, the yield can reach 80%, the enantioselectivity can reach 85%, and the method can be applied to industrial preparation.
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Paragraph 0082-0086
(2021/05/22)
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- Cycloaddition Reactions of Alkene Radical Cations using Iron(III)-Phenanthroline Complex
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Single electron oxidation of electron-rich alkenes using the iron(III)-phenanthroline complex produced electrophilic alkene radical cations, which promoted efficient radical cation [2+1] cycloaddition reactions with diazo compounds. Subsequent chain propagation afforded tri- and tetra-substituted cyclopropanes. This methodology was also expanded to [3+2] cycloaddition reactions with vinyl diazoesters, validating this sustainable, first-row transition metal iron system for the single electron redox reactions. (Figure presented.).
- Cho, Yong Hyun,Kim, Jae Hyung,An, Hyeju,Ahn, Kwang-Hyun,Kang, Eun Joo
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supporting information
p. 2183 - 2188
(2020/04/29)
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- Total Syntheses of All Six Chiral Natural Pyrethrins: Accurate Determination of the Physical Properties, Their Insecticidal Activities, and Evaluation of Synthetic Methods
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Chiral total syntheses of all six insecticidal natural pyrethrins (three pyrethrin I and three pyrethrin II compounds) contained in the chrysanthemum (pyrethrum) flower were performed. Three common alcohol components [(S)-cinerolone, (S)-jasmololone, and (S)-pyrethrolone] were synthesized: (i) straightforward Sonogashira-type cross-couplings using available (S)-4-hydroxy-3-methyl-2-(2-propynyl)cyclopent-2-en-1-ones (the prallethrin alcohol) for (S)-cinerolone (overall 52% yield, 98% ee) and (S)-pyrethrolone (overall 54% yield, 98% ee) and (ii) traditional decarboxylative-aldol condensation and lipase-catalyzed optical resolution for (S)-jasmololone (overall 16% yield, 96% ee). Two counter acid segments [(1R,3R)-chrysanthemic acid (A) and (1R,3R)-second chrysanthemic acid precursor (B)] were prepared: (i) C(1) epimerization of ethyl (±)-chrysanthemates and optical resolution using (S)-naphthylethylamine to afford A (96% ee) and (ii) concise derivatization of A to B (96% ee). All six pyrethrin esters (cinerin I/II, jasmolin I/II, and pyrethrin I/II) were successfully synthesized utilizing an accessible esterification reagent (TsCl/N-methylimidazole). To investigate the stereostructure-activity relationship, all four chiral stereoisomers of cinerin I were synthesized. Three alternative syntheses of (±)-jasmololone were investigated (methods utilizing Piancatelli rearrangement, furan transformation, and 1-nitropropene transformation). Insecticidal activity assay (KD50 and IC50) against the common mosquito (Culex pipiens pallens) revealed that (i) pyrethrin I > pyrethrin II, (ii) pyrethrin I (II) > cinerin I (II) ? jasmolin I (II), and (iii) "natural" cinerin I ? three "unnatural" cinerin I compounds (apparent chiral discrimination).
- Ashida, Yuichiro,Kawamoto, Momoyo,Matsuo, Noritada,Moriyama, Mizuki,Tanabe, Yoo
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p. 2984 - 2999
(2020/03/24)
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- High-yield ethyl chrysanthemate preparation method
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The invention belongs to the technical field of chemical processes, and specifically relates to a high-yield ethyl chrysanthemate preparation method. The high-yield ethyl chrysanthemate preparation method comprises the following steps: (1) diazotization: a step of adding water, glycine ethyl ester acid salt, glacial acetic acid and dimethyl carbonate as solvents into a diazotization kettle, dropwisely adding a sodium nitrite aqueous solution into the diazotization kettle, and carrying out a reaction so as to a diazo liquid; (2) cyclization: a step of putting 2,5-dimethyl-2,4-hexadiene into a cyclization kettle, and carrying out a reaction with cuprous chloride as a catalyst so as to obtain a cyclized solution; (3) desolventizing: a step of sending the cyclized solution into a high-yield desolventizing tower to remove the solvents so as to obtain a crude ethyl chrysanthemate product; and (4) distillation: a step of putting the crude ethyl chrysanthemate product into a distillation kettle, and carrying out vacuum distillation so as to obtain the high-purity ethyl chrysanthemate. The high-yield ethyl chrysanthemate preparation method provided by the invention has the following beneficial effects: when the dimethyl carbonate is used as a solvent, a diazotization reaction can be carried out more completely, so the loss of raw materials is reduced; and meanwhile, the yield of ethyl chrysanthemate in the subsequent cyclization reaction can be improved.
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Paragraph 0037-0080
(2020/12/08)
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- Bottom-Up Synthesis of Acrylic and Styrylic RhII Carboxylate Polymer Beads: Solid-Supported Analogs of Rh2(OAc)4
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We have developed a short and efficient bottom-up synthesis of acrylic and styrylic polymer beads containing dirhodium(II) tetracarboxylates. The solid supported dirhodium(II) tetracarboxylate catalysts were synthesized in as little as two steps overall from dirhodium tetratrifluoroacetate and commercially available carboxylic acids, making the bottom-up approach a viable alternative to the post-modification approach commonly used. The dirhodium(II) tetracarboxylate polymer beads have a convenient size (ca. 100 μm), are easy to handle, and can be considered solid-supported analogs of Rh2(OAc)4. Beads generated from dirhodium(II) tetracarboxylates with four polymerizable carboxylate ligands displayed the best catalytic performance and compared favorably to Rh2(OAc)4 in benchmarked cyclopropanation reactions. The results imply that the cumbersome synthesis of monomeric dirhodium(II) tetracarboxylates with mixed ligands systems can be avoided and that immobilized dirhodium(II)-catalysts with a higher degree of crosslinking is a viable option to catalysts linked in an anchor-like fashion. We demonstrate recovery and recycling, and a potential use of the beads as catalysts in a cyclopropanation reaction towards the insecticide chrysanthemic acid.
- Levchenko, Vladimir,Sundsli, B?rd,?ien-?degaard, Sigurd,Tilset, Mats,Hansen, Finn K.,Bonge-Hansen, Tore
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supporting information
p. 6150 - 6157
(2018/11/23)
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- Cobalt-Catalyzed Reductive Dimethylcyclopropanation of 1,3-Dienes
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Dimethylcyclopropanes are valuable synthetic targets that are challenging to access in high yield using Zn carbenoid reagents. Herein, we describe a cobalt-catalyzed variant of the Simmons–Smith reaction that enables the efficient dimethylcyclopropanation of 1,3-dienes using a Me2CCl2/Zn reagent mixture. The reactions proceed with high regioselectivity based on the substitution pattern of the 1,3-diene. The products are vinylcyclopropanes, which serve as substrates for transition-metal-catalyzed ring-opening reactions, including 1,3-rearrangement and [5+2] cycloaddition. Preliminary studies indicate that moderately activated monoalkenes are also amenable to dimethylcyclopropanation under the conditions of cobalt catalysis.
- Werth, Jacob,Uyeda, Christopher
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supporting information
p. 13902 - 13906
(2018/10/02)
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- Preparing method of cis, trans-ethyl 2, 2-dimethyl-3-(1-isobutenyl)cyclopropane-1-carboxylate
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The invention discloses a method of preparing cis, trans-ethyl 2,2-dimethyl-3-(1-isobutenyl)cyclopropane-1-carboxylate, comprising of making the ethyl glycinate hydro and sodium nitrite in the solvent diazo-react without additional addition of organic acid or mineral acid to get ethyl diazoacetate which is to react with the 2,5-Dimethyl-2,4-hexadiene under the catalyst effect and then be desolvated and rectificated to get ethyl chrysanthemumate.The invention is easy to use with high production yield and high contents.
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Paragraph 0014; 0015; 0016
(2017/08/27)
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- Polyoxometalates: Powerful catalysts for atom-efficient cyclopropanations
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The polyoxometalate-based catalytic cyclopropanation of olefins by ethyl diazoacetate (EDA) is reported. The outstanding catalyst productivity (TONs up to 100,000) and the use of equimolar EDA/olefin ratio confer to the methodology a high sustainability. Preliminary mechanistic investigations are also discussed.
- Boldini, Irene,Guillemot, Geoffroy,Caselli, Alessandro,Proust, Anna,Gallo, Emma
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supporting information; experimental part
p. 2365 - 2370
(2010/12/25)
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- Cu and Au metal-organic frameworks bridge the gap between homogeneous and heterogeneous catalysts for alkene cyclopropanation reactions
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The copper and gold metal-organic frameworks (MOFs) [Cu3(BTC) 2(H2O)3]n, [Cu3(BTC) 2] (BTC = benzene-1,3,5-tricarboxylate), and IRMOF-3-SI-Au are active and reusable solid catalysts for the cyclopropanation of alkenes with high chemo- and diastereoselectivities. This type of material gives better results than previous solid catalysts while working together with the homogeneous catalysts. These MOFs can help to bridge the gap between homogeneous and heterogeneous catalysis.
- Corma, Avelino,Iglesias, Marta,Llabres i Xamena, Francesc X.,Sanchez, Felix
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experimental part
p. 9789 - 9795
(2010/11/02)
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- OPTICALLY ACTIVE COPPER CATALYST COMPOSITION
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There is provided an optically active copper catalyst composition comprising(a) an optically active salicylideneaminoalcohol represented by the formula (1): wherein R1 and R2 are the same or different, and independently represent a substituted or unsubstituted lower alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group; X1 and X2 are the same or different, and independently represent a hydrogen atom, a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, a cyano group or a halogen atom; and * represents an asymmetric center, provided that both of X1 and X2 don't represent hydrogen atoms,(b) a monovalent or divalent copper compound, and(c-1) a lithium compound or(c-2) a compound selected from aluminum compounds having Lewis acidity, titanium compounds having Lewis acidity, boron compounds having Lewis acidity, zirconium compounds having Lewis acidity and hafnium compounds having Lewis acidity; and a process for producing an optically active cyclopropane compound by using the same.
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- Reactions of vinylcyclopropane epoxides with samarium and phosphorus iodides
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Samarium diiodide on one hand, diphosphorus tetraiodide, and phosphorus triiodide on the other, react with vinylcyclopropane epoxides to produce either allylic alcohols or vinylcyclopropanes resulting from cyclopropane ring-opening or deoxygenation of the epoxide, respectively. Georg Thieme Verlag Stuttgart.
- Krief, Alain,Dumont, Willy,Baillieul, Diane
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p. 2688 - 2690
(2007/10/03)
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- Synthesis and characterisation of new polynuclear copper(I) pyrazolate complexes and their catalytic activity in the cyclopropanation of olefins
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The reaction of [Cu(CH3CN)4](BF4) with racemic pyrazole-3,5-dicarboxylic acid di-sec-butyl ester (3,5-dicarbo-sec-butoxypyrazole, Hdcsbpz) or with pyrazole-3,5-di-ter-butyl (3,5-di-ter-butylpyrazole, Hdtbpz) quantitatively yields the new [Cu(dcsbpz)]4 and [Cu(dtbpz)]4 complexes, respectively. Crystals of [Cu(dcsbpz)]4 are triclinic, P1?, a =10.9748(7), b =11.8399(8), c =26.5575(17) ?, α =100.605(2), β =90.783(2), γ =105.362(2)°; [Cu(dtbpz)]4·CH2Cl2 is monoclinic, P21/n, a =10.902(3), b =19.200(3), c =25.772(4) ?, β =93.86(2)°. Both species contain cyclic tetrameric molecules, with the heterocyclic ligands binding in the common N,N′-exo-bidentate mode; however, the shape and geometry of the inner Cu4 moiety is remarkably different, as highlighted, for example, by the absolute values of the 1,2 and 1,3 (non-bonding) Cu?Cu interactions. These polynuclear copper(I) pyrazolate complexes catalyse the conversion of alkenes into the corresponding cyclopropane derivatives with interesting diastereomeric excesses. Aiming at the evaluation of their catalytic activities, a systematic study of the cyclopropanation reactions in the presence of ethyl diazoacetate has been performed.
- Maspero, Angelo,Brenna, Stefano,Galli, Simona,Penoni, Andrea
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p. 123 - 129
(2007/10/03)
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- Copper(I)-homoscorpionate catalysts for the preferential, kinetically controlled cis cyclopropanation of α-olefins with ethyl diazoacetate
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In situ prepared copper catalysts TpxCu (Tpx = homoscorpionate) catalyze the olefin cyclopropanation reaction using ethyl diazoacetate as the carbene source. Very high values of both activity and diastereoselectivity toward the cis isomer have been obtained for styrene, α-methylstyrene, 1-hexene, 1-octene, vinyl acetate, n-butyl vinyl ether, 2,5-dimethyl-2,4-hexadiene, and 3,3-dimethyl-1-butene. The effect of the temperature in the diastereoselectivity was almost negligible within the range -10 to +30°C. Kinetic studies have allowed us to propose that the homoscorpionate ligand might act in a dihapto form during the catalytic process. This transformation seems to operate under kinetic control, where the formation of the cis isomer would govern the reaction rate.
- Diaz-Requejo, M. Mar,Caballero, Ana,Belderrain, Tomas R.,Nicasio, M. Carmen,Trofimenko, Swiatoslaw,Perez, Pedro J.
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p. 978 - 983
(2007/10/03)
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- Optically active bisoxazoline compounds, production and use thereof
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An optically active bisoxazoline compound of the formula [I]: wherein R1 represents alkyl group, cycloalkyl group, aralkyl group, phenyl group which may be substituted or alkoxy group and two geminal alkyl groups may be joined together to form a cyclic structure; R2 represents alkyl group, cycloalkyl group, aralkyl group, phenyl group which may be substituted; R3 represents hydrogen atom, (C2-C4)alkyl group or cycloalkyl group; and the asterisk * represents an asymmetric carbon atom.
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- Process for producing optically active cyclopropanecaboxylic acid esters
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A process for producing an optically active cyclopropanecarboxylic acid ester which is characterized by reacting a prochiral olefin with a diazoacetic acid ester in the presence of a copper complex obtained by reacting an optically active bisoxazoline ligand with a copper compound.
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- Reaction of Allyl Nonafluorobutyl Sulfones with Michael Acceptors, Synthesis of Chrysanthemic Acid Derivatives
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3-Methyl-2-butenyl nonafluorobutyl sulfone (4) reacts with ethyl 3-methyl-2-butenoate (ethyl senecioate, 2) to form ethyl chrysanthemate (3). 5-Methyl-1-(2-methyl-1-propenyl)-3-pentenyl nonafluorobutyl sulfone (5) is formed as a byproduct.The nonaflone 4 is prepared by reaction of 3-methyl-2-butenyl bromide (9) with sodium nonafluorobutanesulfinate or by treating isoprene with nonafluorobutanesulfinic acid.Reaction of 3,3-dichloro-2-propenyl nonafluorobutyl sulfone (12) with ethyl senecioate (2) does not lead to ethyl permethrinate (13), instead self-condensation products of 12, the cyclopropyl sulfone 15 and the disulfone 16 are obtained.
- Hanack, Michael,Auchter, Anneliese,Wunde, Christian,Stoll, Theodor
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p. 853 - 858
(2007/10/02)
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- SYNTHESIS WITH MANGANIC SALTS; PART III: SYNTHESIS OF 1,4-DIKETONES THROUGH MANGANIC ACETATE-MEDIATED ADDITION OF KETONE TO ISOPENTENYL SULFONES. ACETOXYLATION OF Β,Γ-UNSATURATED KETONES BY MANGANOUS AND CUPRIC ACETATES
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Conditions have been found to selectively add ketones to isopentenyl sulfones.The major product, a ketone bearing a methylene group at the γ position, gave upon ozonolysis the corresponding 1,4-diketone.The usefulness of the overall process was illustrated by the efficient syntheses of jasmone and of one half of pyrenophorine.The γ-acetoxy conjugated enones that invariably formed during these additions resulted from the oxidation of an isomeric β,γ-unsaturated ketone by manganous and cupric acetates.Such an acetoxylation has been used to prepare 6β-acetoxy-cholestenone from cholesterol and also to prepare chrysanthemic acid.
- Breuilles, Pascal,Uguen, Daniel
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p. 705 - 720
(2007/10/02)
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- Cyclopropanation process
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A process for producing a cyclopropane derivative comprising contacting a diazo compound and an olefinically unsaturated compound in the presence of a catalytic amount of copper cation-exchanged perfluorinated ion exchange polymer is disclosed.
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- Cyclopropanation of olefins by ethyl diazoacetate: copper- and copper-complex-containing X-zeolites as the catalysts
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Cyclopropanation of olefins by ethyl diazoacetate has been carried out making use of the catalytic action of Cu-loaded X-type zeolites upon the decomposition of ethyl diazoacetate.The activity of the NaCuX zeolites is linearly dependent upon the Na-exchange level.Compared to conventional copper catalysts, the zeolite catalysts give rise to relatively low amounts of polymeric side-product which is assumed to be formed at the outer zeolite surface.The stereoselectivity obtained with the zeolite catalysts does not deviate significantly from that obtained using copper salts.Zeolite X, loaded with chiral copper complexes, gives rise to only minor asymmetric induction upon cyclopropanation of 1,1-dichloro-4-methyl-1,3-pentadiene with ethyl diazoacetate.
- Oudejans, J.C.,Kaminska, J.,Dalen, A. C. Kock-van,Bekkum, H. van
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p. 421 - 427
(2007/10/02)
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- TRANSITION-METAL-CATALYSED REACTIONS OF DIAZOESTERS : SYNTHESIS OF CHRYSANTHEMIC AND PERMETHRIC ACID ESTERS BY CYCLOPROPANATION OF CONJUGATED DIENES
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Pyrethroid precursors (permethric and chrysanthemic acid esters) are efficiently synthesized by rhodium(II)-catalysed cyclopropanation of the properly substituted conjugated diene.Reaction selectivities depend on both the catalyst counter-ion and the diazoester alkoxy-group (carbene precursor) and are attributed to non-bonded interactions.
- Demonceau, A.,Noels, A. F.,Anciaux, A. J.,Hubert, A. J.,Teyssie, P.
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p. 949 - 952
(2007/10/02)
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- REVISION DE STRUCTURE D'UN BENZOATE ALLYLIQUE, INTERMEDIAIRE DE SYNTHESE D'ACIDES CHRYSANTEMIQUES
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The previously described allylic benzoate - an intermediate in a synthesis of ethyl chrysanthemates 1 (Tetr.Lett. 1976, 2441) - was not the secondary compound 4 but the tertiary isomer 3.
- Ficini, J.,Falou, S.,d'Angelo, J.
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p. 375 - 376
(2007/10/02)
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- EXCEPTIONALLY EFFECTIVE CATALYSIS OF CYCLOPROPANATION REACTIONS BY THE HEXARHODIUM CARBONYL CLUSTER
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Hexadecacarbonylhexarhodium exhibits exceptional activity as a cyclopropanation catalyst in reactions between ethyl diazoacetate and alkenes that are remarkably free of competing processes.
- Doyle, Michael P.,Tamblyn, William H.,Buhro, William E.,Dorow, Roberta L.
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p. 1783 - 1786
(2007/10/02)
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