- Catalytic synthesis of octadiene-1,7 from ethylene and cyclohexene
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A new method is proposed for the synthesis of octadiene-1,7 by co-metathesis of ethylene and cyclohexene (ethenolysis). The reaction is carried out in a flow setup at elevated pressures using an original NH4ReO4/Al2O3 heterogeneous catalyst. At the first stage of the reaction, carbenes are formed as intermediates. The optimal conditions of the co-metathesis process were found. The catalyst developed provides the cyclohexene conversion about 25 wt. %, i.e. close to the thermodynamic limit, at the selectivity to octadiene-1,7 close to 100% (99.9%). The catalyst shows good stability in six cycles including 5-h catalytic runs with intermediate regenerative treatments.
- Kustov,Furman
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Read Online
- Redox Activity of Pyridine-Oxazoline Ligands in the Stabilization of Low-Valent Organonickel Radical Complexes
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Low-valent organonickel radical complexes are common intermediates in cross-coupling reactions and metalloenzyme-mediated processes. The electronic structures of N-ligand supported nickel complexes appear to vary depending on the actor ligands and the coordination number. The reduction products of a series of divalent (pyrox)Ni complexes establish the redox activity of pyrox in stabilizing electron-rich Ni(II)-alkyl and -aryl complexes by adopting a ligand-centered radical configuration. The reduced pyrox imparts an enhanced trans-influence. In contrast, such redox activity was not observed in a (pyrox)Ni(I)-bromide species. The excellent capability of pyrox in stabilizing electron-rich Ni species resonates with its proclivity in promoting the reductive activation of C(sp3) electrophiles in cross-coupling reactions.
- Wagner, Clifton L.,Herrera, Gabriel,Lin, Qiao,Hu, Chunhua T.,Diao, Tianning
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Read Online
- Mechanistic Characterization of (Xantphos)Ni(I)-Mediated Alkyl Bromide Activation: Oxidative Addition, Electron Transfer, or Halogen-Atom Abstraction
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Ni(I)-mediated single-electron oxidative activation of alkyl halides has been extensively proposed as a key step in Ni-catalyzed cross-coupling reactions to generate radical intermediates. There are four mechanisms through which this step could take place: oxidative addition, outer-sphere electron transfer, inner-sphere electron transfer, and concerted halogen-atom abstraction. Despite considerable computational studies, there is no experimental study to evaluate all four pathways for Ni(I)-mediated alkyl radical formation. Herein, we report the isolation of a series of (Xantphos)Ni(I)-Ar complexes that selectively activate alkyl halides over aryl halides to eject radicals and form Ni(II) complexes. This observation allows the application of kinetic studies on the steric, electronic, and solvent effects, in combination with DFT calculations, to systematically assess the four possible pathways. Our data reveal that (Xantphos)Ni(I)-mediated alkyl halide activation proceeds via a concerted halogen-atom abstraction mechanism. This result corroborates previous DFT studies on (terpy)Ni(I)- and (py)Ni(I)-mediated alkyl radical formation, and contrasts with the outer-sphere electron transfer pathway observed for (PPh3)4Ni(0)-mediated aryl halide activation. This study of a model system provides insight into the overall mechanism of Ni-catalyzed cross-coupling reactions and offers a basis for differentiating electrophiles in cross-electrophile coupling reactions.
- Diccianni, Justin B.,Katigbak, Joseph,Hu, Chunhua,Diao, Tianning
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supporting information
p. 1788 - 1796
(2019/01/26)
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- Photoredox-Assisted Reductive Cross-Coupling: Mechanistic Insight into Catalytic Aryl-Alkyl Cross-Couplings
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Here, we describe a photoredox-assisted catalytic system for the direct reductive coupling of two carbon electrophiles. Recent advances have shown that nickel catalysts are active toward the coupling of sp3-carbon electrophiles and that well-controlled, light-driven coupling systems are possible. Our system, composed of a nickel catalyst, an iridium photosensitizer, and an amine electron donor, is capable of coupling halocarbons with high yields. Spectroscopic studies support a mechanism where under visible light irradiation the Ir photosensitizer in conjunction with triethanolamine are capable of reducing a nickel catalyst and activating the catalyst toward cross-coupling of carbon electrophiles. The synthetic methodology developed here operates at low 1 mol % catalyst and photosensitizer loadings. The catalytic system also operates without reaction additives such as inorganic salts or bases. A general and effective sp2-sp3 cross-coupling scheme has been achieved that exhibits tolerance to a wide array of functional groups.
- Paul, Avishek,Smith, Mark D.,Vannucci, Aaron K.
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p. 1996 - 2003
(2017/02/26)
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- Enzymatic Oxidative Tandem Decarboxylation of Dioic Acids to Terminal Dienes
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The biocatalytic oxidative tandem decarboxylation of C7–C18dicarboxylic acids to terminal C5–C16dienes was catalyzed by the P450 monooxygenase OleT with conversions up to 29 % for 1,11-dodecadiene (0.49 g L–1). The sequential nature of the cascade was proven by the fact that decarboxylation of intermediate C6–C11ω-alkenoic acids and heptanedioic acid exclusively gave nonconjugated 1,4-pentadiene; scale-up allowed the isolation of 1,15-hexadecadiene and 1,11-dodecadiene; the system represents a short and green route to terminal dienes from renewable dicarboxylic acids.
- Dennig, Alexander,Kurakin, Sara,Kuhn, Miriam,Dordic, Andela,Hall, Mélanie,Faber, Kurt
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supporting information
p. 3473 - 3477
(2016/07/29)
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- Cobalt-Catalyzed Csp3?Csp3Homocoupling
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An efficient and easy method for Csp3?Csp3homocoupling was developed using cobalt bromide as catalyst. A series of functionalized alkyl bromides and alkyl chlorides were coupled in high yields under mild conditions. This reaction seems to involve a radical intermediate. (Figure presented.).
- Cai, Yingxiao,Qian, Xin,Gosmini, Corinne
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supporting information
p. 2427 - 2430
(2016/08/16)
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- Catalytic decarbonylation of biosourced substrates
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Linear α-olefins (LAO) are one of the main targets in the field of surfactants, lubricants, and polymers. With the depletion of petroleum resources, the production of LAO from renewable feedstocks has gained increasing interest in recent years. In the present study, we demonstrated that Ir catalysts were suitable to decarbonylate a wide range of biosourced substrates under rather mild conditions (160 °C, 5 h reaction time) in the presence of potassium iodide and acetic anhydride. The resulting LAO were obtained with good conversion and selectivity provided that the purity of the substrate, the nature of the ligand, and the amounts of the additives were controlled accurately. The catalytic system could be recovered efficiently by using a Kugelrohr distillation apparatus and recycled.
- Ternel, Jérémy,Lebarbé, Thomas,Monflier, Eric,Hapiot, Frédéric
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p. 1585 - 1592
(2015/05/20)
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- METHOD FOR PRODUCING OCTADIENE
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An object of the present invention is to provide a process for producing an octadiene from 2,7-octadienyl formate in an industrially useful manner in which palladium can maintain its catalytic activity for a long period of time. More specifically, the present invention relates to a process for producing an octadiene which includes the steps of continuously adding 2,7-octadienyl formate into a reaction system in which a mixture of a palladium compound, a tertiary organophosphorus compound and a solvent is present; and subjecting the 2,7-octadienyl formate to reaction while continuously distilling off a reaction product containing the resulting octadiene out of the reaction system.
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Paragraph 0030
(2015/03/31)
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- METHOD FOR PRODUCING HIGH PURITY TERMINAL OLEFIN COMPOUND
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An industrially advantageous method for producing a high purity terminal olefin is disclosed, comprising the steps of (a) contacting a mixture comprising a terminal olefin represented by formula (1): and one or more corresponding internal olefins as impurities, with a brominating agent in the presence of water or an alcohol, to convert the internal olefin(s) to compound(s) having a higher boiling point than the terminal olefin; and (b) purifying the terminal olefin by distillation from the reaction mixture.
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Page/Page column 5
(2012/02/06)
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- Thermolysis studies on platinacycloalkane complexes
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Thermal decomposition studies on platinacycloalkanes of the type Pt(CH 2)mL2 (where m = 6,7,8,10 and L2 = dppp {1,3-bis(diphenylphosphino)propane}, dppe {1,2-bis(diphenylphosphino) ethane} or L = PPh3, tBu3P) are described. The results reveal that the organic product distribution depends on various factors such as the nature of ligand, the metal system, the mode of decomposition, the ring size and the temperature. Possible mechanistic pathways for the formation of various products are discussed. These platinacycloalkanes can be used as models for metallacycloalkane intermediates in catalytic reactions.
- Zheng, Feng,Sivaramakrishna, Akella,Moss, John R.
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scheme or table
p. 2457 - 2465
(2011/06/26)
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- Nickel-Catalyzed reductive cross-Coupling of unactivated alkyl halides
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A Ni-catalyzed reductive approach to the cross-coupling of two unactivated alkyl halides has been successfully developed. The reaction works efficiently for primary and secondary halides, with at least one being bromide. The mild reaction conditions allow for excellent functional group tolerance and provide the C(sp3)-C(sp3) coupling products in moderate to excellent yields.
- Yu, Xiaolong,Yang, Tao,Wang, Shulin,Xu, Hailiang,Gong, Hegui
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supporting information; experimental part
p. 2138 - 2141
(2011/06/22)
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- Synthesis and reactivity of platinacycloalkanes
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Novel large platinacycloalkane compounds containing 19- and 21- membered rings of the type L2Pt(CH2)n (L2 = dppp and n = 18, 20) are synthesized through the ring closing metathesis (RCM) reaction of bis(1-alkeny
- Sivaramakrishna, Akella,Makhubela, Banothile C.E.,Moss, John R.,Smith, Gregory S.
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experimental part
p. 1627 - 1633
(2010/09/05)
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- METHOD FOR PRODUCING DIENES BY HYDRODIMERIZATION
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The invention relates to a process for preparing substituted or unsubstituted 1,7-diolefins by hydrodimerizing non-cyclic olefins having at least two conjugated double bonds in the presence of a reducing agent and of a catalyst, wherein the catalyst used is a metal-carbene complex.
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Page/Page column 6
(2009/12/05)
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- Method for the production of 1,7-octadiene and use thereof
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The invention relates to a method for the production of 1,7 octadiene by reacting metathesis of cyclohexene with ethylene. The invention also relates to the production of 1,10-decandiol by hydroformulating 1,7 octadiene produced according to said method. The invention further relates to a method for the production of muscone or olefinically unsaturated analogs thereof using 1,10 decandiol which is obtainable in said manner.
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- PROCESS FOR THE PREPARATION OF 1-OCTENE
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Process in two steps for the preparation of 1-octene starting from butadiene which comprises: a first step (a) in which the bis-hydrodimerization of butadiene to 1,7-octadiene is effected in the presence of a catalyst based on a palladium complex containing one or more tri-substituted monodentate phosphines, in an aprotic polar solvent optionally containing an organic base; a second step (b) in which the partial catalytic hydrogenation of 1,7-octadiene to 1-octene is effected, the above process being characterized in that: (i) in the first step the aprotic polar solvent is selected from disubstituted cyclic ureas; (ii) in the second step the catalyst is selected from non- supported ruthenium complexes having general formula (I I): RuXmLn (I I).
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Page/Page column 13-14
(2008/06/13)
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- PROCESS FOR PRODUCING 1-OCTENE FROM BUTADIENE IN THE PRESENCE OF TITANIUM CATALYSTS
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A method is described for the preparation of 1-octene starting from butadiene, wherein in a first step (a) the bis-hydrodimerization of butadiene to 1,7-octadiene is effected in the presence of a catalyst based on palladium containing one or more tri-substituted monodentate phosphines, in an aprotic polar solvent, in a second step (b) the partial catalytic hydrogenation of 1,7-octadiene to 1-octene is effected in the presence of a titanium compound activated with one or more metal alkyls of group 13 (selected from boron, aluminum, gallium, indium).
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Page/Page column 11-12
(2008/06/13)
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- METHOD FOR THE PRODUCTION OF 1.7-OCTADIENE AND USE THEREOF
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The invention relates to a method for the production of 1.7 octadiene by reacting metathesis of cyclohexene with ethylene. The invention also relates to the production of 1.10-decandiol by hydroformulating 1.7 octadiene produced according to said method. The invention further relates to a method for the production of muscone or olefinically unsaturated analogs thereof using 1.10 decandiol which is obtainable in said manner.
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Page/Page column 72-73
(2010/02/11)
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- METHOD FOR THE TELOMERISATION OF NON-CYCLIC OLEFINS
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The invention relates to a method for the telomorisation of non-cyclic olefins, comprising at least two conjugated double bonds (I) or mixtures which contain said olefins, with nucleophiles (II). A metal-carbene complex is used as a catalyst.
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Page/Page column 19-20
(2008/06/13)
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- Reduction of organic halides with lanthanum metal: A novel generation method of alkyl radicals
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Results of the reaction of alkyl halides with lanthanum metal have been shown. The reduction of alkyl iodide with 1/3 equiv of lanthanum metal efficiently proceeded to give the corresponding reductive dimerized products along with the formation of reduction and dehydroiodination products. In the case of alkyl bromides and chlorides, the reaction did not proceed under the same reaction conditions as that of alkyl iodides; however, the reaction was dramatically promoted by the addition of a catalytic amount of iodine. A reaction pathway including alkyl radicals was suggested.
- Nishino, Toshiki,Watanabe, Toshihisa,Okada, Mitsuo,Nishiyama, Yutaka,Sonoda, Noboru
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p. 966 - 969
(2007/10/03)
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- Flash vacuum pyrolysis over magnesium. Part 1 - Pyrolysis of benzylic, other aryl/alkyl and aliphatic halides
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Flash vacuum pyrolysis over a bed of freshly sublimed magnesium on glass wool results in efficient coupling of benzyl halides to give the corresponding bibenzyls. Where an ortho halogen substituent is present further dehalogenation gives some dihydroanthracene and anthracene. Efficient coupling is also observed for halomethylnaphthalenes and halodiphenylmethanes while chlorotriphenylmethane gives 4,4′-bis(diphenylmethyl)biphenyl. By using α,α′-dihalo-o-xylenes, benzocyclobutenes are obtained in good yield, while the isomeric α,α′-dihalo-p-xylenes give a range of high thermal stability polymers by polymerisation of the initially formed p-xylylenes. Other haloalkylbenzenes undergo largely dehydrohalogenation where this is possible, in some cases resulting in cyclisation. Deoxygenation is also observed with haloalkyl phenyl ketones to give phenylalkynes as well as other products. With simple alkyl halides there is efficient elimination of HCl or HBr to give alkenes. For aliphatic dihalides this also occurs to give dienes but there is also cyclisation to give cycloalkanes and dehalogenation with hydrogen atom transfer to give alkenes in some cases. For 5-bromopent-1-ene the products are those expected from a radical pathway but for 6-bromohex-1-ene they are clearly not. For 2,2-dichloropropane and 1,1-dichloropropane elimination of HCl occurs but for 1,1-dichlorobutane, -pentane and -hexane partial hydrolysis followed by elimination of HCl gives E, E-, E,Z- and Z,Z- isomers of the dialk-1-enyl ethers and fully assigned 13C NMR data are presented for these. With 6-chlorohex-1-yne and 7-chlorohept-1-yne there is cyclisation to give methylenecycloalkanes and -cycloalkynes. The behaviour of 1,2-dibromocyclohexane and 1,2-dichlorocyclooctane under these conditions is also examined. Various pieces of evidence are presented that suggest that these processes do not involve generation of free gas-phase radicals but rather surface-adsorbed organometallic species.
- Aitken, R. Alan,Hodgson, Philip K.G.,Morrison, John J.,Oyewale, Adebayo O.
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p. 402 - 415
(2007/10/03)
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- Synthesis and Properties of (η3-1-Methylallyl)palladium(II) Formates as Models of Intermediates in the Palladium-Catalyzed Reductive Cleavage of Allylic Carboxylates and Carbonates with Formic Acid
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In order to gain insight into the mechanism of the regioselective formation of alkenes in the palladium-catalyzed reductive cleavage of allylic carboxylates or carbonates with formic acid, two types of (η3-1-methylallyl)palladium formates (P1 and P2 types) have been prepared as simple models of catalytic intermediates. The P1 type is a neutral complex coordinated with one tertiary phosphine ligand and a formato ligand: [Pd(η3-MeCHCHCH2)(O2CH)(L)] (L = PMePh2, PMe2Ph, PMe3, P(o-tolyl)3); the P2 type is a cationic complex bearing two tertiary phosphine ligands and a formate counter anion: [Pd(η3-MeCHCHCH2)L2]+CO2H- (L = PMePh2, PMe2Ph, PMe3). The structures and dynamic behavior of the complexes in solution have been examined in detail by NMR spectroscopy. Studies on the thermolysis of the P1 and P2-type complexes have clearly provided the following mechanistic viewpoints: (1) 1-butene and 2-butene are formed from the P1 species; (2) butadiene is liberated from the P2 species; (3) the ratio of 1-butene to 2-butene increases as the bulkiness of phosphine ligand increases. A mechanism involving two geometrical isomers of [Pd(η3-MeCHCHCH2)(H)(L)], which are formed by decarboxylation of the P1-type complexes, has been proposed for the formation of butenes.
- Oshima, Masato,Sakamoto, Toshiaki,Maruyama, Yooichiroh,Ozawa, Fumiyuki,Shimizu, Isao,Yamamoto, Akio
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p. 453 - 464
(2007/10/03)
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- Stereospecific rhenium catalyzed desulfurization of thiiranes
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Methyltrioxorhenium catalyzes the efficient and stereospecific desulfurization of thiiranes by triphenylphosphine at room temperature, moreso when MTO has been pretreated with hydrogen sulfide, with a Re(v) species as the active form of the catalyst.
- Jacob, Josemon,Espenson, James H.
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p. 1003 - 1004
(2007/10/03)
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- Kinetics of the Thermal Isomerizations of Gaseous Cycloheptene and Cyclooctene
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Single-pulse shock tube kinetic studies of the thermal isomerizations of gaseous cycloheptene (CHEP) and cis-cyclooctene (COCT), and static reactor isomerizations of COCT at lower temperatures, have revealed a mechanistic dissimilarity in the two superficially analogous cycloalkene to, α,ω-alkadiene reactions observed.At 1035-1256 K, CHEP produced mostly vinylcyclopentane, log10(k,s-1) = 15.1 (+/- 0.7) - 69.7 (+/- 3.3) x 103/4.576T, and some 1,6-heptadiene.From COCT, heated over the range 610-1091 K, the dominant product was 1,7-octadiene, log10(k,s-1) = 13.8 (+/- 0.2) -54.6 (+/- 0.5) x 103/4.576T, with small amounts of vinylcyclohexane formed at the higher temperatures, log10(k,s-1) = 15.2 (+/- 0.3) - 64.4 (+/- 1.2) x 103/4.576T.The activation energy for the COCT isomerization to 1,7-octadiene is too low to associate with formation of a diradical, but is consistent with a concerted retro-ene mechanism.The higher activation energy isomerization to vinylcyclohexane, however, passes through a diradical transition structure.In contrast, the structure of CHEP is not adaptable to a concerted retro-ene precess, and both 1,6-heptadiene and vinylcyclopentane are formed through diradical-mediated reactions.
- Kalra, Bansi L.,Afriyie, Yau,Brandt, Benjamin,Lewis, David K.,Baldwin, John E.
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p. 8142 - 8146
(2007/10/02)
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- Fragmentation Patterns in the Gas-Phase Pyrolysis of Some Bi- and Tri-cyclic Sulfolanes Related to the 8-Thiabicyclonon-3-ene 8,8-Dioxide Ring System
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Depending upon the degree of ring strain, the thermal breakdown of cis-8-thiabicyclonon-3-ene 8,8-dioxide 5 and related ring systems in the gas phase follows widely differing pathways.Decomposition of 5 occurs only under forcing conditions, resulting in complete fragmentation of the sulfolane ring to give a benzene and toluene, while pyrolysis of the 2,5-bridged analogues 6-8 proceeds by a retro-Diels-Alder reaction at much lower temperatures to give 1,3-dienes and the decomposition products of 3-sulfolene, buta-1,3-diene and SO2.Epoxidation of the double bond in the compounds results in a marked change in their thermal fragmentation behaviour; only SO2 is lost to produce novel divinyl epoxides.The corresponding N-ethoxycarbonylaziridines, formed by photolysis of the unsaturated sulfones in ethyl azidoformate, undergo extensive decomposition on pyrolysis and do not yield any useful products.The saturated sulfone 28 gives an expected octa-1,7-diene upon flash vacuum pyrolysis (FVP), but only under relatively severe conditions.Three isomeric diene sulfones 30-32 have also been examined and show a varied pattern of reactivity under FVP conditions.
- Aitken, R. Alan,Cadogen, J. I. G.,Gosney, Ian,Newlands, Stephen
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p. 2301 - 2308
(2007/10/02)
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- A Highly Catalytic and Selective Conversion of Carboxylic Acids to 1-Alkenes of One Less Carbon Atom
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An equimolar mixture of a carboxylic acid and acetic anhydride produces a reagent combination that undergoes a highly efficient decarbonylation/dehydration at 250 deg C using either Pd- or Rh-based catalyst systems, affording excellent yields of the corresponding 1-alkenes of one less carbon atom.
- Miller, Joseph A.,Nelson, Jeffrey A.,Byrne, Michael P.
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- Deazetation of a Bicyclic Azo Compound: Product and Mechanistic Studies
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In the deazetation of 7,8-diazabicyclodec-7-ene 2, the product distributions from direct and sensitised photolyses are different, as would be expected if a spin correlation effect operates.A larger difference, however, is found between the distributions from the two nominally singlet processes, thermolysis and the direct photolysis.Several trivial explanations for this are ruled out, and two explanations are put forward, involving the intermediacy of either a diazenyl biradical or two singlet electronic states of the tetramethylene biradical, cyclooctanediyl.
- Samuel, Christopher J.
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p. 405 - 408
(2007/10/02)
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- Deazetation of a Bicyclic Azo Compound: Resolution of a Stereochemical Ambiguity and Conformational Analysis of a Biradical
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Development of a new approach has permitted a fuller analysis of the stereochemistry of deazetation of the stereospecifically deuteriated azo compound (1d) than could be achieved previously, in that it has proved possible to analyse 2H2>octa-1,7-diene for E,E-, E,Z,-and Z,Z-content.This has given results for the thermal and photochemical reactions that can be rationalised in terms of partial conformational equilibration of the biradical.
- Samuel, Christopher J.
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p. 1259 - 1265
(2007/10/02)
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- Rotational Barriers of Strained Olefines
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For the olefins 1-8 heats of formation have been derived from heats of hydrogenation and force-field calculations, respectively.From the kinetics of their geometrical isomerisation the corresponding values for the transition states were obtained.The rotational barriers, which vary by nearly 30 kcal/mol, can be described by a unique torsional potential (65.9 +/- 0.9 kcal/mol), which is independent of the degree of substitution, if a correction is made for the steric energy contribution in the ground- and transition-states. - Key Words: Rotational barriers / Olefins, strained / Heat of Hydrogenation / Force-field calculation
- Doering, William v. E.,Roth, Wolfgang R.,Bauer, Frank,Breuckmann, Rolf,Ebbrecht, Thomas,at al.
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p. 1263 - 1276
(2007/10/02)
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- Preparation of 1-Alkenes by the Palladium-Catalyzed Hydrogenolysis of Terminal Allylic Carbonates and Acetates with Formic Acid-Triethylamine
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A useful method for the preparation of 1-alkenes from terminal allylic carbonates and acetates by the palladium-catalyzed reaction with formates is described.Formic acid-triethylamine is a suitable reductant.As catalyst, Pd2(dba)3CHCl3-P(n-Bu)3 gave the best result, 0.05-0.2 molpercent being sufficient (turnover 500-2000).Using this method, various 1-alkenes were prepared in good yields with high selectivity.
- Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao
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p. 623 - 627
(2007/10/02)
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- Regio- and Stereo-specific Reduction of Conjugated and Non-conjugated Triple Bonds by Activated Zinc Powder
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Regio- as well as stereo-specific reductions of a wide variety of acetylenic derivatives have been carried out in absolute ethanol with zinc powder activated with 1,2-dibromoethane, and with zinc powder activated successively with dibromoethane and copper(I) bromide, the first reagent being less powerful and more selective than the second one.
- Aerssens, Marc H. P. J.,Brandsma, Lambert
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p. 735 - 736
(2007/10/02)
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- REGIOSELECTIVE SYNTHESIS OF 1-OLEFINS BY PALLADIUM-CATALYZED HYDROGENOLYSIS OF TERMINAL ALLYLIC COMPOUNDS WITH AMMONIUM FORMATE
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Various terminal allylic compounds such as allylic esters, phenyl esters, carbonates, chlorides, and vinyl epoxides react with ammonium or sodium formate to give 1-olefins with high regioselectivity by using palladium-tributylphosphine complex as a catalyst.The reaction offers a useful synthetic method for 1-olefins.
- Tsuji, Jiro,Shimizu, Isao,Minami, Ichiro
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p. 1017 - 1020
(2007/10/02)
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- Unusual Stereochemistry in the Thermal Deazetation of a Bicyclic Azo Compound
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Thermolysis of the stereospecifically deuteriated azo-compound (1D) led to bicyclo-octane (3) with complete retention and octadiene (4) with partial loss of stereochemistry.
- Samuel, Christopher J.
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p. 131 - 132
(2007/10/02)
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- HYDROGENATION OF ALKYNES WITH A PALLADIUM ANCHORED POLYSTYRENE CATALYST
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Treating chloromethylated polystyrene beads with anthranilic acid and then palladium chloride gives a material capable of catalyzing the cis-hydrogenation of alkynes.Hydrogenation of phenylacetylene (10 mmol) with 0.017 g-atom (based on Pd) of catalyst at room temperature and 30 psig for 7.3 h resulted in 82percent styrene and 14percent ethylbenzene.Methylphenylacetylene was converted to cis-1-phenylpropene (60percent) and n-propylbenzene (17percent).Several other alkynes were also converted to cis alkenes.The catalyst is less selective than the Lindlar catalyst, but is air stable and stores well.
- Holy, Norman L.,Shelton, Steven R.
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