- Synthesis of diphenylhexatriene by the Pd-catalyzed dimerization of cinnamyl acetate
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A mild and operationally simple method to synthesize diphenylhexatriene (DPH) is reported. The method relies on the Pd-catalyzed dimerization of cinnamyl acetate and provides efficient access to DPH in a single step.
- Mesganaw, Tehetena,Im, G-Yoon J.,Garg, Neil K.
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- Pd-Catalyzed Cross-Coupling of Organostibines with Styrenes to Give Unsymmetric (E)-Stilbenes and (1 E,3 E)-1,4-Diarylbuta-1,3-dienes and Fluorescence Properties of the Products
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A general and effective palladium-catalyzed cross-coupling of organostibines with styrenes to give (E)-olefins was disclosed. By the use of an organostibine reagent, this method can produce unsymmetric (E)-1,2-diarylethylenes and (1E,3E)-1,4-diarylbuta-1,3-dienes in good yields with high E/Z selectivity and good functional group tolerance. Resveratrol and DMU-212 were synthesized in high yield. The protocol can be extended to the synthesis of (1E,3E,5E)-1,6-diphenylhexa-1,3,5-triene in 40% yield. Products 5e, 5f, and 7a showed good photoluminescence quantum yields ranging from 72 to 99%.
- Zhang, Zhao,Zhang, Dejiang,Zhu, Longzhi,Zeng, Dishu,Kambe, Nobuaki,Qiu, Renhua
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supporting information
p. 5317 - 5322
(2021/06/28)
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- Palladium-Catalyzed Three-Component Reaction of 3-(Tri-n- butylstannyl)allyl Acetates, Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ-Substituted Allylic Tin Reagents
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A three-component reaction of 3-(tri-n-butylstannyl)allyl acetates, aldehydes, and triorganoboranes in the presence of a palladium-Xantphos catalyst system predominately gave (E)-anti-homoallylic alcohols with high diastereoselectivity and good to high levels of alkene stereocontrol. An efficient chirality transfer was observed when an enantioenriched substrate was employed. The reaction was initiated by the formation of an allylic gem-palladium/stannyl intermediate, which subsequently underwent allylation of the aldehyde by an allyltributyltin followed by a coupling reaction of the in-situ-generated (E)-vinylpalladium acetate with the triorganoborane.
- Horino, Yoshikazu,Sugata, Miki,Abe, Hitoshi
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p. 1023 - 1028
(2016/04/19)
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- Effect of substituents and conjugated chain length on the UV spectra of α,ω-di-substituted phenyl polyenes
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A series of α,ω-di-substituted phenyl polyenes, p-X-Ph(CH = CH)nPh-p-Y (n = 1, 2, or 3) were synthesized, and their ultraviolet (UV) absorption maximum wavelength were determined. The correlation between molecular structure and the maximum wavelength energy (wavenumber/cm -1) was carried out. The results show that the maximum wavelength energy of the title compounds is mainly affected by both substituent excited-state parameters and maximum wavelength energy of the parent molecule. However, the two influence factors are not independent, and the action of substituent is governed by the parent molecular absorption energy. In the case of the compounds containing NO2 or NH2 groups, the influence of interaction of polarity parameters on the maximum wavelength energy must also be considered. In addition, the exploration was also made for the quantifying correlation of UV absorption maximum wavelength energy with the conjugated polarizability potential CPP replacing the parent molecular absorption energy. And the results indicate that the equation with CPP parameters is more accurate and convenient. Copyright 2013 John Wiley & Sons, Ltd. For the α,ω-di-substituted phenyl polyenes, p-X-Ph(CH = CH)nPh-p-Y (n = 1, 2, or 3), their ultraviolet absorption maximum wavelength energy (wavenumber/cm-1) was mainly affected by both substituent excited-state parameters and maximum wavelength energy of the parent molecule. However, the two influence factors are not independent, and the action of substituent is governed by the parent molecular absorption energy. Copyright
- Cao, Chenzhong,Zhu, Yun,Chen, Guanfan
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p. 834 - 839
(2013/10/01)
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- Z-selective metathesis homocoupling of 1,3-dienes by molybdenum and tungsten monoaryloxide pyrrolide (MAP) complexes
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Molybdenum or tungsten monoaryloxide pyrrolide (MAP) complexes that contain OHIPT as the aryloxide (hexaisopropylterphenoxide) are effective catalysts for homocoupling of simple (E)-1,3-dienes to give (E,Z,E)-trienes in high yield and with high Z selectivities. A vinylalkylidene MAP species was shown to have the expected syn structure in an X-ray study. MAP catalysts that contain OHMT (hexamethylterphenoxide) are relatively inefficient.
- Townsend, Erik M.,Schrock, Richard R.,Hoveyda, Amir H.
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supporting information; experimental part
p. 11334 - 11337
(2012/09/05)
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- Cyclopropanation of strained alkenes by palladium-catalyzed reaction of 3-trimethylsilyl- or 3-pinacolatoboryl-1-arylallyl acetates
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The palladium-catalyzed cyclopropanation of strained alkenes with 3-trimethylsilyl- or 3-pinacolatoboryl-1-arylallyl acetate derivatives is described. This reaction gives cyclopropanation products in good to high yields with a single diastereomer, and the key step is likely to involve the formation of a palladacyclobutene complex from the α-trimethylsilyl- or α-pinacolatoboryl-σ-allylpalladium complex. Copyright
- Horino, Yoshikazu,Homura, Naoki,Inoue, Kana,Yoshikawa, Saori
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p. 828 - 834
(2012/05/04)
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- A highly tunable stereoselective olefination of semistabilized triphenylphosphonium ylides with N -Sulfonyl imines
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The Wittig reaction involving direct olefination of triphenylphosphonium ylides (Ph3PCHR) with aldehydes is arguably the most often used method for alkene synthesis, but in general it yields mixtures of Z- and E-alkenes for semistabilized triphenylphosphonium ylides (R = aryl or vinyl). We have developed a simple and efficient protocol to improve the stereoselectivity significantly by replacing the aldehydes used in the Wittig reaction with N-sulfonyl imines, which possess distinct electronic and steric properties relative to aldehydes. A broad range of aromatic, α,β-unsaturated, and aliphatic imines bearing appropriate N-sulfonyl groups smoothly undergo olefination reaction with various benzylidenetriphenylphosphoranes or allylidenetriphenylphosphoranes under mild reaction conditions to afford an array of both Z- and E-isomers of conjugated alkenes in good to excellent yields and with greater than 99:1 stereoselectivity. Moreover, this tunable protocol has been successfully applied to the highly stereoselective synthesis of two anticancer agents, DMU-212 and its Z-isomer.
- Dong, De-Jun,Li, Hai-Hua,Tian, Shi-Kai
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supporting information; experimental part
p. 5018 - 5020
(2010/06/13)
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- Photoisomerization of all-cis-1,6-diphenyl-1,3,5-hexatriene in the solid state and in solution: A simultaneous three-bond twist process
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Disrotatory bicycle pedals: Irradiation of the title compound in the solid state gives the all-trans isomer directly in a crystal-to-crystal reaction. This threefold cis-trans photoisomerization is proposed to proceed by a two-stage mechanism that is consistent with two simultaneous bicyclepedal processes occurring in disrotatory fashion about the central bond.
- Saltiel, Jack,Papadimitriou, Dimitrios,Krishna, Tallapragada S. R.,Huang, Zhen-Nian,Krishnamoorthy, Govindarahan,Laohhasurayotin, Somchoke,Clark, Ronald J.
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scheme or table
p. 8082 - 8085
(2010/01/16)
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- A novel ambident reactivity of azolylacroleins
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Reaction of azolylacroleins with phosphoranes bearing a conjugated double bond was found to yield either azolyltrienes in?a Wittig reaction, or to undergo cyclization to a dihydrobenzene containing the azole substituent. Transformation with an aza-Wittig reagent gave tetrazolylpyridines. The ambident reactivity was found to be dependent on the substituent of the phosphorane, which was rationalized by ab initio (DFT) calculation of the atomic charges of the reaction centres.
- Nagy, Ildikó,Hajós, Gy?rgy,Riedl, Zsuzsanna,Egyed, Orsolya,Pápai, Imre
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p. 4730 - 4736
(2007/10/03)
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- The effect of vicinyl olefinic halogens on cross-coupling reactions using Pd(0) catalysis
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(trans) 1-Chloro-2-iodoethylene (3), (trans) 1-bromo-2-iodoethylene (4), (trans) 1,2-diiodoethylene (5) and (cis and trans) 1,2-dibromoethylene (11) were reacted under Suzuki, Sonogashira and Negishi cross-coupling conditions using Pd catalysis to obtain mono coupled products. Only olefin template 3 provided the desired coupling products reliably under all reaction conditions. Compound 5 did not provide cross coupled products under any of the reaction conditions used. The Negishi reaction was the only one that worked for templates 4 and 11. Studies indicate that oxidative addition of the most reactive carbon-halogen bond to Pd(0) is followed by elimination of the second halide, when the second halide is a bromide or an iodide. This happens to a much lesser degree when the second halogen is a chloride. Graphical Abstract.
- Organ, Michael G.,Ghasemi, Haleh,Valente, Cory
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p. 9453 - 9461
(2007/10/03)
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- Stereoselective O2-induced photoisomerization of all-trans-1,6-diphenyl-1,3,5-hexatriene
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Irradiation of all-trans-1,6-diphenyl-1,3,5-hexatriene (ttt-DPH) in degassed acetonitrile (AN) gives ctt- and tct-DPH, relatively inefficiently, mainly via isomerization in the singlet excited state. The triplet contribution to the photoisomerization is small due to a very low intersystem crossing yield (φis = 0.01). Central bond isomerization is quenched in the presence of air by a factor of 1.4, consistent with the expected quenching of the lowest singlet and triplet excited states by oxygen. However, the presence of air enhances terminal bond photoisomerization by nearly twofold. Triplet-sensitized ttt-DPH photoisomerization favors tct-DPH formation and is quenched by oxygen. It follows that the interaction of singlet-excited ttt-DPH with O2 suppresses isomerization to tct-DPH but opens a new isomerization pathway to ctt-DPH. The presence of dimethylfuran, a singlet O2 trap, has no effect on the photoisomerization, eliminating the possible involvement of singlet O2 in this new reaction, ttt-DPH radical cations are ruled out as intermediates because the presence of fumaronitrile, which leads to their formation, suppresses both central and terminal bond photoisomerizations. In contrast to acetonitrile, ctt-DPH formation is quenched by oxygen in methylcyclohexane, suggesting the requirement of a polar environment. Strikingly different deuterium isotope effects distinguish the direct and O2-induced photoisomerization pathways. A comparative study of ttt-DPH-d0 with ttt-DPH-d 2 and ttt-DPH-d4, involving deuteration of one and both terminal double bonds, reveals an inverse kinetic isotope effect (k. Hox/kDox = 0.92) for the O 2-induced reaction. An attractive mechanism for the new oxygen-induced photoisomerization involves charge transfer from the S 1 state of ttt-DPH to oxygen followed by collapse of the exciplex to either a zwitterionic or a biradicaloid species through bonding at one of the benzylic positions. Rotation about the new single bond in this intermediate followed by reversion to DPH and O2 gives the observed result.
- Saltiel, Jack,Krishnamoorthy, Govindarajan,Huang, Zhennian,Ko, Dong-Hoon,Wang, Shujun
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p. 673 - 679
(2007/10/03)
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- Mapping the potential energy surfaces of the 1,6-diphenyl-1,3,5- hexatriene ground and triplet states
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The relative energies of the ground state isomers of 1,6-diphenyl- 1,3,5-hexatriene (DPH) in benzene are determined from the temperature dependence of the equilibrium isomer composition obtained with the use of diphenyl diselenide as isomerization catalyst. In the triplet state, DPH exists as an equilibrium mixture of all-trans (ttt), trans,cis,trans (tct), cis,trans,trans (ctt), and cis,cis,trans (cct) isomers. Under degassed conditions, photoisomerization of the triplets is primarily bimolecular, involving a quantum chain process. Oxygen eliminates the quantum chain process by efficient deactivation of DPH triplets thereby revealing the triplet state isomeric composition. The temperature dependencies of the fluorenone-sensitized photoisomerization quantum yields and photostationary states for DPH in air-saturated benzene provide two independent measures of the temperature dependence of the equilibrium contribution of the isomeric triplets. They reveal the relative energies of the DPH triplet isomers. Together with the known 34 kcal/mol triplet energy of ttt-DPH, these results define points on the potential energy surfaces of the ground and triplet states corresponding to the equilibrium geometries of the four observed DpH isomers. At these geometries the two surfaces roughly parallel each other. Complete equilibration of isomeric triplets within 100 ns requires that the energies of triplet biradical transition states be no higher than 40.3 kcal/mol. Estimated radical stabilization energies give 40.2 and 41.6 kcal/mol for the energies of biradical transition states for central and terminal bond isomerization, respectively, in the ground state of ttt-DPH.
- Saltiel, Jack,Crowder, Janell M.,Wang, Shujun
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p. 895 - 902
(2007/10/03)
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- Stereoselective Z,E-photoisomerization of formyl-substituted (E,E,E)-1,6-diphenylhexa-1,3,5-triene in solution
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Direct irradiation of (E,E,E)-1,6-bis(4-formylphenyl)hexa-1,3,5-triene in chloroform under argon atmosphere led to a fast equilibrium between E,E,E(62%) and Z,E,E(38%) isomers. Neither isomers nor photoproducts were detected by HPLC in the photostationary mixture. This is entirely different from the reaction of (E,E,E)-1,6-diphenylhexa-1,3,5-triene on irradiation under similar conditions, in which dimers and solvent adducts were formed via various kinds of Z isomers. The high stereoselectivity observed in the Z,E-photoisomerization of the formyl-substituted diphenylhexatriene can be explained by the assumption that a terminal twisted transient state has a zwitterionic character which is stabilized by the polarization of carbonyl groups.
- Sonoda, Yoriko,Suzuki, Yasuzo
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p. 401 - 404
(2007/10/03)
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- Stereoselective Synthesis of Substituted 1,3,5-Hexatrienes from Diallylic Sulfones
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Substituted 1,3,5-hexatrienes 7 can be prepared in excellent yields and with good stereoselectivity from diallylic sulfones 6 employing a modified Ramberg-Baecklund reaction.
- Cao, Xiao-Ping,Chan, Tze-Lock,Chow, Hak-Fun,Tu, Jingren
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p. 1297 - 1300
(2007/10/02)
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- Pinacol Coupling of Aliphatic Aldehydes Promoted by Niobium (III) Reagent
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NbCl3 (DME) was found to be a useful reagent for the intermolecular pinacol coupling of aliphatic aldehydes.The high anti diastereoselectivity of this reaction (dl / meso >/= 9 / 1) did not depend on the variation in the aldehyde alkyl chain.With respect to intramolecular pinacolization, the loss of the stereoselectivity observed is consistent with the mechanism involving an insertion of the oxo-group into the metal-carbon bond of the intermediate niobiooxirane. - Key Words: Nb(III) reagent; Pinacol coupling; Acetalization; Stereoselectivity
- Szymoniak, Jan,Besancon, Jack,Moise, Claude
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p. 2841 - 2848
(2007/10/02)
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- Synthesis of 5-Methoxy- and 5-(Dialkylamino)bicyclohept-2-en-6-one Derivatives by cine Substitution with Methoxide Anions and Dialkylamines
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exo-7-Chloro-endo-7-phenylbicyclohept-2-en-6-one (5) undergoes cine substitution reactions with methoxide anions and with dialkylamines to give 5-methoxy or 5-dialkylamino derivatives 13, 14, 16-19 in high yield.While attempts directed to an acetalization have failed, the addition of Grignard reagents to the methoxy derivatives proceeds stereoselectively in high yield.Hydrochlorides 20/21 lose amine at 110 deg C to form 2-phenyltropone (22).Thermolysis of diethylamino derivative 24 at 170 deg C (temperature determined by DSC) results in the formation of the dienoaminone 25. - Key Words: Bicyclohept-2-en-6-one, cine substitution / DSC
- Butenschoen, Holger
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p. 137 - 144
(2007/10/02)
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- Alkylvanadium and Alkylniobium Reagents, II. - Niobium-Induced Reductive Carbonyl Dimerization
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NbCl5 reacts with one equivalent of methyllithium or metallic potassium to give a reagent for the transformation of aldehydes, ketones, benzalchloride, and benzotrichloride to symmetrically substituted ethene derivatives (Tab.1).The reagent NbCl5/K (2) is distinctly more reactive than NbCl5/MeLi (1).For the reductive carbonyl dimerization with niobium reagents a mechanism is proposed.Key Words: Reductive carbonyl dimerization / Niobium pentachloride
- Kauffmann, Thomas,Kallweit, Harry
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p. 149 - 151
(2007/10/02)
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- A new general route to 1,2-diarylethylenes, 1,4-diarylbutadienes and 1,6-diarylhexatrienes through cycloaromatization of β-oxodithioacetals
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A new general route for the title olefins 5 a-e, 12, 13, 8a-e and 11 a-e has been developed through nucleophilic addition of respective Grignard reagents i.e. allyl-, benzyl-, 1-(naphthylmethyl) magnesium halides to 5-aryl-1,1-bis(methylthio)pent-4-en-3-ones, 7-aryl-1,1-bis(methylthio)hepta-4,6-dien-3-ones and 9-phenyl-1,lbis(methylthio)nona-4,6,8-trien-3-one followed by cycloaromatization of the resulting 3-substituted 1,1-bis(methylthio)alken-3-ols in the presence of boron trifluoride-diethyl ether complex.
- Rao,Singh,Ila,Junjappa
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p. 1075 - 1077
(2007/10/02)
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- A HIGHLY STEREOSELECTIVE SYNTHESIS OF SUBSTITUTED BUTADIENES AND CONJUGATED POLYENES
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A highly stereoselective synthesis of 1,3-butadienes and its higher enyl analogs has been developed through thermal dehydrative ring opening of cyclopropyl carbinols in dimethylsulphoxide.
- Patro, Balaram,Ila, Hiriyakkanavar,Junjappa, Hiriyakkanavar
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p. 809 - 812
(2007/10/02)
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- Preparation of tricarbonyl(η4-vinylketene)iron(0) complexes from tricarbonyl(η4-vinyl ketone)iron(0) complexes and their subsequent conversion to tricarbonyl(η4-vinylketenimine)iron(0) complexes
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Reaction of tricarbonyl(η4-vinyl ketone)iron(0) complexes (CO)3(PhCH=CHC(R)=O)Fe(O) (R = Me, 1; Bun, 3; But, 5; Ph, 7) with organolithium reagents under an atmosphere of carbon monoxide gave products that were identified as tricarbonyl (η4-vinylketene) iron(0) complexes (CO)3(PhCH=CHC(R)=C=O)Fe(0) (R = Me, 2; Bun, 4; But, 6; Ph, 8) based on a crystal structure analysis of 2. Complex 2 crystallizes in space group P21/c with a = 13.998 (6) A?, b = 7.955 (5) A?, c = 12.935 (5) A?, β = 113.04 (3)°, and Z = 4. A reaction pathway that postulates the intermediacy of a tricarbonyl(η3-vinylcarbene)iron(0) complex, 20, is discussed. Heating the tricarbonyl(η4-vinylketene)iron(0) complexes 6 and 2 with either tert-butyl, cyclohexyl, or 2,6-xylyl isocyanide at 80°C gave tricarbonyl (η4-vinylketenimine) iron(0) complexes (CO)3(PhCH=CHC(R1)= C=NR2)Fe(0) (R1 = R2 = But, 23; R1 = Me, R2 = But, 24; R1 = Me, R2 = C6H11, 25; R1 = Me, R2 = (2,6-Me2)C6H3, 26) via intermediate dicarbonyl(isocyanide)(η4-vinylketene)iron(0) complexes. The intermediacy of tricarbonyl(isocyanide)(η1-vinylcarbene)iron(0) complexes in this reaction is proposed.
- Alcock, Nathaniel W.,Richards, Christopher J.,Thomas, Susan E.
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p. 231 - 238
(2008/10/08)
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- Reductive Coupling of Geminal Dichlorides by Iron(II) Oxalate Dihydrate
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A facile procedure for the quantitative conversion of geminal dichlorides to E olefins with iron(II) oxalate dihydrate in refluxing anhydrous dimethylformamide under a nitrogen atmosphere is described.The coupling proceeds via the corresponding vicinal dichlorides.
- Khurana, Jitender M.,Maikap, Golak C.,Mehta, Sanjay
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p. 731 - 732
(2007/10/02)
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- Pulse Radiolysis Study of Ion Pairing of Diphenylpolyene Radical Anions with Tetrabutylammonium and Sodium Cations in Tetrahydrofuran
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Pulse radiolysis of tetrahydrofuran (THF) solutions of all-trans α,ω-diphenyl-substituted polyenes, such as 1,4-diphenylbuta-1,3-diene, 1,6-diphenylhexa-1,3,5-triene and 1,8-diphenylocta-1,3,5,7-tetraene, has been undertaken in the absence and presence of Bu4NPF6 and NaBPh4.In the presence of the salts, the absorption maxima of the diphenylpolyene radical anions are shifted to shorter wavelengths by ion pairing with Bu4N+ and Na+ as well as that of the trans-stilbene radical anion previously investigated.When Ph(CH=CH)nPH.- (n=1-4) is paired with Bu4N+, the magnitude of the spectroscopic shift is larger for n=2-4 than for n=1.On the other hand, the magnitude of the spectroscopic shift due to the ion pairing with Na+ decreases with increasing n and becomes very small in the case of n=3 or 4.The decay of the radical anions, which is due to neutralization reactions with THF(H+), is retarded by the addition of the salts.The retarding effect of the salts is attributed to the ion pairing of the reactant ions with the counterions derived from the salts.In acetonitrile solution the absorption spectra and the decay rates of the radical anions are not affected by the addition of the salts, demonstrating that the ion pairing is not important in such a polar solvent.Results for the radical anions of pyrene, perylene and triphenylethylene are presented for the sake of comparison.The appreciable spectroscopic shift due to the ion pairing with the large Bu4N+ ion was found to be characteristic of the diphenylpolyene radical anions.
- Aoyama, Takahisa,Yamamoto, Yukio,Hayashi, Koichiro
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p. 3353 - 3358
(2007/10/02)
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- Palladium-Catalyzed Syntheses of Conjugated Trienes
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Conjugated trienes 3 and 5 have been prepared by the palladium-catalyzed reaction of alkenes 2 with fumaryl chloride (1) and (E)-5-phenyl-2,4-pentadienoyl chloride (4), respectively, in the presence of N-ethylmorpholine.
- Kasahara, Akira,Izumi, Taeko,Kudou, Naoto
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p. 704 - 705
(2007/10/02)
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- REACTION OF ARYLMETHANESULFONYL AND STYRYLMETHANESULFONYL CHLORIDES WITH TRIETHYLAMINE
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A series of arylmethanesulfonyl chlorides were treated with triethylamine in THF to give stilbenes in excellent yields.Workup of the mixtures below 10 deg C permits isolation of stilbene episulfones which on warming decompose to yield the corresponding stilbenes stereospecifically.Application of the reaction to 9-fluorenylsulfonyl chloride affords bifluorenylidene, while trans-styrylmethanesulfonyl chloride gives 4,5-dihydro-4,5-diphenylthiepin 1,1-dioxide and 1,6-diphenylhexatriene.
- Nakayama, Juzo,Tanuma, Mitsuru,Honda, Yoshiko,Hoshino, Masamatsu
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p. 4553 - 4556
(2007/10/02)
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- Palladium-Catalyzed Syntheses of Aryl Polyenes
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The palladium-catalyzed arylation reaction has been employed to prepare a variety of mono- and diaryl 1,3-dienes and 1,3,5-trienes.The yields were good when electron withdrawing substituents were present in the aryl groups but only poor to fair when electron-donating groups were involved.Monoaryl dienes and trienes reacted well with all types of aryl halides to give mixed diaryl derivatives. 2-Bromostyrene reacts with phenylhexatriene to form 1,8-diphenyloctatetraene and with hexatriene to form 1,10-diphenyldecapentaene, but both only in about 15percent yield.
- Mitsudo, Taki-aki,Fischetti, William,Heck, Richard F.
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p. 1640 - 1646
(2007/10/02)
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