- A convergent approach to indolines and indanes
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Radical addition of a xanthate to an N-allylanilide or to a substituted 4-aryl-1-butene followed by cyclisation onto the aromatic ring provide the corresponding indoline or indane respectively.
- Ly, Thi-My,Quiclet-Sire, Beatrice,Sortais, Benoit,Zard, Samir Z.
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Read Online
- Palladium(II)-Catalyzed Aminotrifluoromethoxylation of Alkenes: Mechanistic Insight into the Effect of N-Protecting Groups
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An efficient palladium-catalyzed regioselective 5-exo aminotrifluoromethoxylation of alkenes has been established herein, which provides a practical route towards the synthesis of OCF3-containing pyrrolidines. tert-Butyloxycarbonyl (Boc) as an amino protecting group plays a significant role in both the chemo- and regioselectivities. In addition, preliminary mechanistic studies reveal that the amino protecting group of substrates and the counter anion of palladium catalyst play critical roles in reaction efficiency presumably due to an isomerization of alkyl- Pd(II) intermediates. Moreover, the asymmetric 5-exo aminotrifluoromethoxylation reaction has also been achieved by introducing a sterically bulky pyridinyl-oxazoline ligand.
- Chen, Chaohuang,Chen, Pinhong,Hou, Chuanqi,Liu, Guosheng
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supporting information
p. 346 - 350
(2020/05/25)
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- Ni-Catalyzed hydrocyanation of alkenes with formamide as the cyano source
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CN generation from formamide dehydration! A novel Ni-catalyzed hydrocyanation of various alkenes to provide aliphatic nitriles is developed by generating hydrocyanic acid in situ from safe and readily available formamide. Excellent linear or branched regio-selectivity, wide substrate scope, cheap and stable nickel salt as a pre-catalyst, a safe cyano source, slow generation of CN to obviate catalyst deactivation and convenient experimental operation would render this hydrocyanation attactive for laboratory synthesis of aliphatic nitriles.
- Shu, Xiao,Jiang, Yuan-Yuan,Kang, Lei,Yang, Luo
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supporting information
p. 2734 - 2738
(2020/06/17)
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- Rational design of efficient steric catalyst for isomerization of 2-methyl-3-butenenitrile
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The catalytic isomerization of 2-methyl-3-butenenitrile (2M3BN), a model reaction in the DuPont process, has been performed using NiL4 (L=tri-O-p-tolyl phosphite) as a catalyst. The lowered catalytic activity in the isomerization with coexistence of 2-pentenenitrile (2PN) and 2-methyl-2-butenenitrile (2M2BN) indicates that both 2PN and 2M2BN are the catalyst inhibitors, and the quantitative relationship between the conversion of 2M3BN and the content of 2M2BN and 2PN is provided. DFT calculation results suggest that the inhibition effect is attributed to the generation of dead-end intermediates (2PN)NiL2 and (2M2BN)NiL2, both of which take nickel atom out of the catalytic cycle in the isomerization process. To suppress the inhibition effect, new catalytic intermediates are rationally designed based on their computational %Vbur. An efficient method that adding extra ligand 1, 5-bis(diphenylphosphino)pentane (dppp5) to the NiL4 catalyst is selected experimentally. Compared to the results obtained with NiL4 as catalyst, the (dppp5)NiL2 increases the conversion of 2M3BN from 74.5 % to 93.4 % at 3 h of reaction and provides a high selectivity to 3PN (> 98 %) at optimal conditions.
- Han, Minghan,Liu, Kaikai,Wang, Tiefeng
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- I2-Mediated oxidative bicyclization of 4-pentenamines to prolinol carbamates with CO2 incorporating oxyamination of the C=C bond
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A metal-free oxyamination reaction of alkenes with ambient CO2 is reported. In the presence of I2 and DBU, CO2 is applied in situ as a protecting group to regulate the nucleophilicity of the amino group and facilitate the bicyclization of 4-pentenamines with high chemoselectivity. Moreover, this reaction provided a feasible approach to prepare prolinol carbamates with good tolerance of functional groups and high efficiency under mild conditions.
- Wang, Sheng,Zhang, Xiaowei,Cao, Chengyao,Chen, Chao,Xi, Chanjuan
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supporting information
p. 4515 - 4519
(2017/10/13)
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- Design of Core-Pd/Shell-Ag Nanocomposite Catalyst for Selective Semihydrogenation of Alkynes
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We designed core-Pd/shell-Ag nanocomposite catalyst (Pd@Ag) for highly selective semihydrogenation of alkynes. The construction of the core-shell nanocomposite enables a significant improvement in the low activity of Ag NPs for the selective semihydrogenation of alkynes because hydrogen is supplied from the core-Pd NPs to the shell-Ag NPs in a synergistic manner. Simultaneously, coating the core-Pd NPs with shell-Ag NPs results in efficient suppression of overhydrogenation of alkenes by the Pd NPs. This complementary action of core-Pd and shell-Ag provides high chemoselectivity toward a wide range of alkenes with high Z-selectivity under mild reaction conditions (room temperature and 1 atm H2). Moreover, Pd@Ag can be easily separated from the reaction mixture and is reusable without loss of catalytic activity or selectivity.
- Mitsudome, Takato,Urayama, Teppei,Yamazaki, Kenji,Maehara, Yosuke,Yamasaki, Jun,Gohara, Kazutoshi,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information
p. 666 - 670
(2016/02/18)
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- Green, Multi-Gram One-Step Synthesis of Core–Shell Nanocomposites in Water and Their Catalytic Application to Chemoselective Hydrogenations
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We devise a new and green route for the multi-gram synthesis of core–shell nanoparticles (NPs) in one step under organic-free and pH-neutral conditions. Simply mixing core and shell metal precursors in the presence of solid metal oxides in water allowed for the facile fabrication of small CeO2-covered Au and Ag nanoparticles dispersed on metal oxides in one step. The CeO2-covered Au nanoparticles acted as a highly efficient and reusable catalyst for a series of chemoselective hydrogenations, while retaining C=C bonds in diverse substrates. Consequently, higher environmental compatibility and more efficient energy savings were achieved across the entire process, including catalyst preparation, reaction, separation, and reuse.
- Urayama, Teppei,Mitsudome, Takato,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information
p. 17962 - 17966
(2016/12/16)
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- Photoredox-Catalyzed Intramolecular Aminodifluoromethylation of Unactivated Alkenes
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A photoredox catalyzed aminodifluoromethylation of unactivated alkenes has been developed in which HCF2SO2Cl is used as the HCF2 radical source. Sulfonamides were active nucleophiles in the final step of a tandem addition/oxidation/cyclization process to form pyrrolidines, and esters were found to cyclize to form lactones. Thus, a variety of pyrrolidines and lactones were obtained in moderate to excellent yield. In order for the cyclization reactions to be efficient, a combination of a copper catalyst (Cu(dap)2Cl) and silver carbonate was crucial to suppressing a competing chloro, difluoroalkylation process.
- Zhang, Zuxiao,Tang, Xiaojun,Thomoson, Charles S.,Dolbier, William R.
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supporting information
p. 3528 - 3531
(2015/07/28)
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- PROCESS FOR ISOMERIZATION OF CIS-2-PENTENENITRILE TO 3-PENTENENITRILES
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Discontinuous or continuous isomerization of cis-2-pentenenitrile to 3-pentenenitriles, comprises isomerizing cis-2-pentenenitrile with tertiary amine compounds (I) and their mixtures. Discontinuous or continuous isomerization of cis-2-pentenenitrile to 3-pentenenitriles, comprises isomerizing cis-2-pentenenitrile with tertiary amine compounds of formula (I) and their mixtures. R1, R2 : H, linear or branched 1-5C-alkyl, 5-7C-cycloalkyl, hydroxyethyl or ethylene group bridging two N. [Image].
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Paragraph 0066-0068
(2017/01/02)
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- Enantioselective diamination with novel chiral hypervalent iodine catalysts
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Vicinal diamines constitute one the most important functional motif in organic chemistry because of its wide occurrence in a variety of biological and pharmaceutical molecules. We report an efficient metal-free, highly stereoselective intramolecular diamination using a novel chiral hypervalent iodine reagent together with its application as an efficient catalyst for the synthesis of diamines.
- Mizar, Pushpak,Laverny, Aragorn,El-Sherbini, Mohammad,Farid, Umar,Brown, Michael,Malmedy, Florence,Wirth, Thomas
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supporting information
p. 9910 - 9913
(2014/08/18)
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- Process for Isomerization of CIS-2-Pentenenitrile to 3-Pentenenitriles
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The present invention relates to an improved process for batchwise or continuous isomerization of cis-2-pentenenitrile to 3-pentenenitriles in the presence of 1,4-diazabicyclo[2.2.2]octane as catalyst.
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Paragraph 0051
(2013/11/06)
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- Cu(II)-mediated aminooxygenation of alkenylimines and alkenylamidines with TEMPO
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A method for the synthesis of oxymethyl dihydropyrroles (pyrrolines) and dihydroimidazoles has been developed via Cu(II)-mediated intramolecular aminooxygenation of alkenylimines and alkenylamidines, respectively, with 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO). Georg Thieme Verlag Stuttgart · New York.
- Sanjaya, Stephen,Chua, Sze Hui,Chiba, Shunsuke
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supporting information; experimental part
p. 1657 - 1661
(2012/07/17)
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- ORGANOPHOSPHORUS COMPOUNDS BASED ON TETRAPHENOL (TP)-SUBSTITUTED STRUCTURES
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The invention relates to the synthesis of tetraphenol-substituted structures, in particular meta-substituted xylenes. Said tetraphenol-type structures are reacted to obtain organic phosphorus compounds, in particular organophosphites. The invention further relates to the production of catalytically active compositions which contain transition metals in addition to the aforementioned organic phosphorus compounds. According to another subject matter of the invention, said catalytically active compositions are used in chemical reactions with small molecules, e.g. HCN, CO, hydrogen, and amines.
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Page/Page column 14-15
(2012/08/08)
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- Vapor-phase Beckmann rearrangement of cyclohexanone oxime over halide cluster catalysts
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When a silica gel-supported tungsten halide cluster with an octahedral metal framework, (H3O)2[(W6Cl 8)Cl6]·6H2O/SiO2, is treated in a helium stream in the temperature range 250-350 °C, catalytic activity for the Beckmann rearrangement of cyclohexanone oxime develops. Niobium and tantalum clusters with the same metal framework also catalyze the reaction. Cyclopentanone oxime and acetone oxime also undergo Beckmann rearrangements over the tungsten cluster. The weak Br?nsted acidity (H0 ≈ +1.5) of the hydroxo ligand, which is developed on the activated cluster, is favorable for the rearrangement.
- Nagashima, Sayoko,Kamiguchi, Satoshi,Ohguchi, Satoshi,Chihara, Teiji
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experimental part
p. 135 - 138
(2012/02/03)
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- NICKEL METAL COMPOSITIONS AND NICKEL COMPLEXES DERIVED FROM BASIC NICKEL CARBONATES
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Nickel-metal-containing solids for use in manufacturing nickel metal complexes are disclosed. The nickel-metal-containing solids are made by reducing basic nickel carbonates. By varying the molar ratios of carbonates and bicarbonates to nickel salts, the methods provide basic nickel carbonates that produce superior nickel metal-containing solids that react more effectively with phosphorous-containing ligands. The phosphorous containing ligands can be both monodentate and bidentate phosphorous-containing ligands.
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Page/Page column 9
(2011/08/22)
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- PROCESS FOR MAKING AND REFINING 3-PENTENENITRILE, AND FOR REFINING 2-METHYL-3-BUTENENITRILE
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The invention provides an integrated, continuous process for the production of 3-pentenenitrile, the refining of 3-pentenenitrile, and the refining of 2-methyl-3-butenenitrile, the process comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a butadiene-containing feed, and a catalyst composition, wherein the catalyst composition comprises a zero-valent nickel and at least one bidentate phosphorus-containing ligand selected from the group consisting of a phosphite, a phosphonite, a phosphinite, a phosphine, a mixed phosphorus-containing ligand, and combination thereof; (b) maintaining a residence time in the reaction zone sufficient to convert about 95% or more of the hydrogen cyanide and to produce a reaction mixture comprising 3-pentenenitrile and 2-methyl-3-butenenitrile, wherein the 2-methyl-3-butenenitrile concentration is maintained below about 15 weight percent of the total mass of the reaction mixture; (c) distilling the reaction mixture to obtain a first stream comprising 1,3-butadiene, a second stream comprising 3-pentenenitrile, 2-methyl-3-butenenitrile, (Z)-2-methyl-2-butenenitrile, and optionally 1,3-butadiene, and a third stream comprising the catalyst composition; (d) distilling the second stream to obtain a fourth stream comprising 1,3-butadiene, a fifth stream comprising 2-methyl-3-butenenitrile, (Z)-2-methyl-2-butenenitrile, and optionally 1,3-butadiene, and a sixth stream comprising 3-pentenenitrile; and (e) distilling the fifth stream to obtain a seventh stream comprising 1,3-butadiene, an eighth stream comprising (Z)-2-methyl-2-butenenitrile, and a ninth stream comprising 2-methyl-3-butenenitrile.
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Page/Page column 23-24
(2009/07/25)
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- Intramolecular hydroamination of aminoalkenes by calcium and magnesium complexes: A synthetic and mechanistic study
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The β-diketiminate-stabilized calcium amide complex [{ArNC(Me)CHC(Me)NAr}Ca{N(SiMe3)2}-(THF)] (Ar = 2,6-diisopropylphenyl) and magnesium methyl complex [{ArNC(Me)CHC(Me)NAr}Mg(Me) (THF)] are reported as efficient precatalysts for hydroamination/cyclization of aminoalkenes. The reactions proceeded under mild conditions, allowing the synthesis of five-, six-, and seven-membered heterocyclic compounds. Qualitative assessment of these reactions revealed that the ease of catalytic turnover increases (i) for smaller ring sizes (5 > 6 > 7), (ii) substrates that benefit from favorable Thorpe-Ingold effects, and (iii) substrates that do not possess additional substitution on the alkene entity. Prochiral substrates may undergo diastereoselective hydroamination/cyclization depending upon the position of the existing stereocenter. Furthermore, a number of minor byproducts of these reactions, arising from competitive alkene isomerization reactions, were identified. A series of stoichiometric reactions between the precatalysts and primary amines provided an important model for catalyst initiation and suggested that these reactions are facile at room temperature, with the reaction of the calcium precatalyst with benzylamine proceeding with ΔG°(298 K) = -2.7 kcal mol-1. Both external amine/amide exchange and coordinated amine/amide exchange were observed in model complexes, and the data suggest that these processes occur via low-activation-energy pathways. As a result of the formation of potentially reactive byproducts such as hexamethyldisilazane, calcium-catalyst initiation is reversible, whereas for the magnesium precatalyst, this process is nonreversible. Further stoichiometric reactions of the two precatalysts with 1-amino-2,2-diphenyl-4-pentene demonstrated that the alkene insertion step proceeds via a highly reactive transient alkylmetal intermediate that readily reacts with N-H σ bonds under catalytically relevant conditions. The results of deuterium-labeling studies are consistent with the formation of a single transient alkyl complex for both the magnesium and calcium precatalysts. Kinetic analysis of the nonreversible magnesium system revealed that the reaction rate depends directly upon catalyst concentration and inversely upon substrate concentration, suggesting that substrate-inhibited alkene insertion is rate-determining.
- Crimmin, Mark R.,Arrowsmith, Merle,Barrett, Anthony G. M.,Casely, Ian J.,Hill, Michael S.,Procopiou, Panayiotis A.
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supporting information; experimental part
p. 9670 - 9685
(2011/03/20)
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- PROCESS FOR MAKING 3-PENTENENITRILE BY HYDROCYANATION OF BUTADIENE
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The invention provides a continuous process for the production of 3-pentenenitrile, comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a 1,3-butadiene-containing feed, and a catalyst precursor composition, wherein the cata
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Page/Page column 9; 9-10; 10
(2008/06/13)
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- PROCESS FOR MAKING 3-PENTENENITRILE BY HYDROCYANATION OF BUTADIENE
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The invention provides a continuous process for the production of 3-pentenenitrile comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a butadiene-containing feed, and a catalyst precursor composition, wherein the catalyst
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Page/Page column 6; 6-7; 7
(2008/06/13)
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- Solvent effects and activation parameters in the competitive cleavage of C-CN and C-H bonds in 2-methyl-3-butenenitrile using [(dippe)NiH]2
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The reaction of [(dippe)NiH]2 with 2-methyl-3-butenenitrile (2M3BN) in solvents spanning a wide range of polarities shows significant differences in the ratio of C-H and C-CN activated products. C-H cleavage is favored in polar solvents, whereas C-C cleavage is favored in nonpolar solvents. This variation is attributed to the differential solvation of the transition states, which was further supported through the use of sterically bulky solvents and weakly coordinating solvents. Variation of the temperature of reaction of [(dippe)NiH]2 with 2M3BN in decane and N,N-dimethylformamide (DMF) allowed for the calculation of Eyring activation parameters for the C-CN activation and C-H activation mechanisms. The activation parameters for the C-H activation pathway were ΔH? = 11.4 ± 5.3 kcal/mol and ΔS? = -45 ± 15 e.u., compared with ΔH? = 17.3 ± 2.6 kcal/mol and ΔS ? = -29 ± 7 e.u. for the C-CN activation pathway. These parameters indicate that C-H activation is favored enthalpically, but not entropically, over C-C activation, implying a more ordered transition state for the former.
- Swartz, Brett D.,Reinartz, Nicole M.,Brennessel, William W.,Garcia, Juventino J.,Jones, William D.
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experimental part
p. 8548 - 8554
(2009/02/03)
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- Chiral neutral zirconium amidate complexes for the asymmetric hydroamination of alkenes
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Aminations with amidates: The first C2-symmetric amidate complexes of zirconium were used for catalytic asymmetric hydroaminations of amino alkenes to prepare chiral gem-disubstituted pyrrolidines with up to 93 % ee (see scheme). The modular nature of the chiral complexes facilitates their preparation and screening as catalysts. (Chemical Equation Presented).
- Wood, Mark C.,Leitch, David C.,Yeung, Charles S.,Kozak, Jennifer A.,Schafer, Laurel L.
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p. 354 - 358
(2007/10/03)
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- Copper(II) carboxylate promoted intramolecular diamination of terminal alkenes: Improved reaction conditions and expanded substrate scope
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The copper(II) carboxylate promoted diamination reaction has been improved by the use of the organic soluble copper(II) neodecanoate [Cu(ND)2]. Cu(ND)2 allowed the less-polar solvent dichloroethane (DCE) to be used, and as a consequence, decomposition of less-reactive substrates could be avoided. High diastereoselectivity was observed in the synthesis of 2,5-disubstituted pyrrolidines. Ureas, bis(anllines), and α-amido pyrroles derived from 2-allylaniline could also participate in the diamination reaction.
- Zabawa, Thomas P.,Chemler, Sherry R.
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p. 2035 - 2038
(2008/02/02)
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- Catayzed vapor-phase hydrocyanation of diolefinic compounds
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A catalysed vapor-phase process for the hydrocyanation of acyclic diolefinic compounds to olefinic nitriles in which the olefinic double bond is not conjugated to the triple bond of the cyano group, wherein a supported catalyst composition comprising at least one multidentate phosphite ligand and zero-valent nickel is preferably used with specially selected or treated supports.
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Page/Page column 7-8
(2008/06/13)
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- 3,3′-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination
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Chiral 3,3′-bis(trisarylsilyl)-substituted binaphtholate rare earth metal complexes (R)-[Ln{Binol-SiAr3}(o-C6H 4CH2NMe2)(Me2NCH2Ph)] (Ln = Sc, Lu, Y; Binol-SiAr3 = 3,3′-bis(trisarylsilyl)-2,2′- dihydroxy-1,1′-binaphthyl; Ar = Ph (2-Ln), 3,5-xylyl (3-Ln)) and (R)-[La{Binol-Si(3,5-xylyl)3}{E(SiMe3)2}(THF) 2] (E = CH (4a), N (4b)) are accessible via facile arene, alkane, and amine elimination. They are efficient catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, giving TOF of up to 840 h -1 at 25 °C for 2,2-diphenyl-pent-4-enylamine (5c) using (R)-2-Y. Enantioselectivities of up to 95% ee were achieved in the cyclization of 5c with (R)-2-Sc. The reactions show apparently zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, but rates depend on total amine concentrations. Activation parameters for the cyclization of pent-4-enylamine using (R)-2-Y (ΔH(S)? = 57.4-(0.8) kJ mol-1 and ΔS(S)? = -102(3) J K-1 mol-1; ΔH(R)? = 61.5(0.7) kJ mol-1 and ΔS(R)? = -103(3) J K-1 mol -1) indicate a highly organized transition state. The binaphtholate catalysts were also applied to the kinetic resolution of chiral α-substituted aminoalkenes with resolution factors f of up to 19. The 2,5-disubstituted aminopentenes were formed in 7:1 to ≥50:1 trans diastereoselectivity, depending on the size of the α-substituent of the aminoalkene. Rate studies with (S)-1-phenyl-pent-4-enylamine ((S)-15e) gave the activation parameters for the matching (ΔH? = 52.2(2.8) kJ mol -1, ΔS? = -127(8) J K-1 mol-1 using (S)-2-Y) and mismatching (ΔH? = 57.7(1.3) kJ mol -1, ΔS? = -126(4) J K-1 mol-1 using (R)-2-Y) substrate/catalyst combination. The absolute configuration of the Mosher amide of (2S)-2-methyl-4,4-diphenyl-pyrrolidine and (2R)-methyl-(5S)- phenyl-pyrrolidinium chloride, prepared from (S)-15e, were determined by crystallographic analysis. Catalyst (R)-4a showed activity in the anti-Markovnikov addition of n-propylamine to styrene.
- Gribkov, Denis V.,Hultzsch, Kai C.,Hampel, Frank
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p. 3748 - 3759
(2007/10/03)
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- METHOD FOR PRODUCING 3-PENTENENITRILE
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The invention relates to a method for producing 3-pentenenitrile, said method being characterised by the following steps: (a) 1,3-butadiene is reacted with hydrogen cyanide on at least one catalyst to obtain a flow (1) containing 3-pentenenitrile, 2-methyl-3-butenenitrile, the at least one catalyst, and 1,3-butadiene; (b) the flow (1) is distilled in a column to obtain a top product flow (2) rich in 1,3-butadiene, and a bottom product flow (3) that is poor in 1,3-butadiene and contains 3-pentenenitrile, the at least one catalyst, and 2-methyl-3-butenenitrile; (c) the flow (3) is distilled in a column to obtain a top product flow (4) containing 1,3-butadiene, a flow (5) in a side-tap of the column, containing 3-pentenenitrile and 2-methyl-3-butenenitrile, and a bottom product flow (6) containing the at least one catalyst; and (d) the flow (5) is distilled to obtain a top product flow (7) containing 2-methyl-3-butenenitrile, and a bottom product flow (8) containing 3-pentenenitrile.
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Page/Page column 35-38; sheet 5
(2008/06/13)
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- PRODUCTION OF 3-PENTENENITRILE FROM 1,3-BUTADIENE
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The invention relates to a method for producing 3-pentenenitrile by means of the hydrocyanation of 1,3-butadiene, whereby 1,3-butadiene is reacted with hydrogen cyanide in the presence of at least one catalyst, and the resulting flow is purified by distillation, the bottom temperature not exceeding 140 °C during the distillation.
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Page/Page column 25-29; sheet 2
(2008/06/13)
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- METHOD FOR PRODUCING LINEAR PENTENENITRILE
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The invention relates to a method for producing 3-pentenenitrile, characterised by the following steps: (a) isomerisation of an educt stream containing 2-methyl-3-butenenitrile on at least one dissolved or dispersed isomerisation catalyst to form a stream (1), which contains the isomerisation catalyst(s), 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile; (b) distillation of the stream (1) to obtain a stream (2) as the overhead product, which contains 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile and a stream (3) as the bottom product, which contains the isomerisation catalyst(s); (c) distillation of the stream (2) to obtain a stream (4) as the overhead product, which is enriched with (Z)-2-methyl-2-butenenitrile in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2)) and a stream (5) as the bottom product, which is enriched with 3-pentenenitrile and 2-methyl-3-butenenitrile in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2); (d) distillation of stream (5) to obtain a stream (6) as the bottom product, which contains 3-pentenenitrile and a stream (7) as the head product, which contains 2-methyl-3-butenenitrile.
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Page/Page column 72-76; sheet 2
(2008/06/13)
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- STERICALLY HINDERED CHELATE PHOSPHINITE-PHOSPHITE LIGAND, CATALYST, COMPRISING AT LEAST ONE NICKEL(0) COMPLEX STABILIZED BY SAID LIGAND AND METHOD FOR PRODUCTION OF NITRILES
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The invention relates to phosphinite phosphites I of formula 1, 2, 3, 4, 5 or 6 and mixtures thereof, wherein R1, R2, R4 independently represent an alkyl or alkylene group with 1 to 8 carbon atoms, provided that at least one of the groups R1, R2, R4 is different from H; R5 to R22 independently represent H, an alkyl or alkylene group with 1 to 8 carbon atoms; R3 is H, methyl or ethyl; X is F, Cl or CF3, if n = 1 or 2 and X is H, if n = 0.
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Page/Page column 20
(2008/06/13)
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- Sterically demanding diphosphonite ligands - Synthesis and application in nickel-catalyzed isomerization of 2-methyl-3-butenenitrile
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The synthesis of a novel class of sterically demanding diphosphonites 1-8, based on rigid backbones, is described. The starting materials are all commercially available and the methodology allows for a modular approach. All ligands have been fully characterized, including an X-ray crystal structure for compound 1, 4,5-bis{di[(2-terr-butyl)phenyl]phosphonito}-9,9-dimethylxanthene. The coordination of these diphosphonite ligands towards Ni(II) and Ni(0) precursors is investigated, both by NMR spectroscopy as well as X-ray crystallography and compared with the behaviour of diphosphine ligands such as Xantphos. The molecular structure for complex 9, trans-[NiBr2(1)] is described in detail. The nickel-catalyzed isomerization of 2-methyl-3- butenenitrile to 3-pentenenitrile is studied, a relevant step in the industrially important hydrocyanation of butadiene (the DuPont adiponitrile process). Good activities and selectivities to the desired 3-pentenenitrile are obtained in this reversible C-C bond activation reaction.
- Van Der Vlugt, Jarl Ivar,Hewat, Alison C.,Neto, Samuel,Sablong, Rafael,Mills, Allison M.,Lutz, Martin,Spek, Anthony L.,Mueller, Christian,Vogt, Dieter
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p. 993 - 1003
(2007/10/03)
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- Method of producing nitrile compounds
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The present invention relates to the manufacture of nitrile compounds from unsaturated organic compounds by reaction with hydrogen cyanide. It relates more particularly to the manufacture of nitrile compounds of use in the synthesis of adiponitrile, an important chemical intermediate in the manufacture of major chemical compounds, such as hexamethylenediamine and ε-caprolactam. The invention provides a process for the manufacture of organic compounds comprising at least one nitrile functional group by carrying out a hydrocyanation reaction between hydrogen cyanide and an organic compound comprising at least one ethylenic unsaturation. This reaction is carried out in the presence of a catalytic system comprising a metal element chosen from the group consisting of nickel, platinum and palladium and an organophosphorus ligand, the reaction medium additionally comprising an ionic liquid in the liquid state at least at the temperature at which the hydrocyanation reaction is carried out.
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- Method for making nitrile compounds from ethylenically unsaturated compounds
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The invention concerns a method for hydrocyanation of ethylenically unsaturated organic compounds comprising at least a nitrile function. The invention provides a method for hydrocyanation of an ethylenically unsaturated hydrocarbon compound by reacting in liquid medium the hydrogen cyanide in the presence of a catalyst comprising a metal element selected among transition metals and an organophosphorous ligand, characterised in that the organophosphorous ligand is a furylphosphine. The invention is in particular useful for synthesizing adiponitrile from butadiene.
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- Hydrocyanation method for ethylenically unsaturated organic compounds
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The invention concerns a method for hydrocyanation of ethylenically unsaturated organic compounds into compounds comprising at least a nitrile function. More particularly, it concerns a method for hydrocyanation of organic compounds comprising at least a ethylenical bond by reacting hydrogen cyanide, in the presence of a catalytic system comprising a transition metal and an organophosphorus ligand. The organophosphorus ligand is a compound with monophosphanorbornadiene structure. The invention concerns in particular hydrocyanation of butadiene into adiponitrile.
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- Kinetic resolution of chiral aminoalkenes via asymmetric hydroamination/cyclisation using binaplitholate yttrium complexes
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Chiral binaphtholate yttrium aryl complexes are highly active and enantioselective catalysts for the asymmetric hydroamination of aminoalkenes, as well as the kinetic resolution of α-substituted 1-aminopent-4-enes to give trans-2,5-disubstituted pyrrolidines with good enantiomeric excess and high krel.
- Gribkov, Denis V.,Hultzsch, Kai C.
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p. 730 - 731
(2007/10/03)
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- Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions
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A polymeric, phosphorus-containing composition made by heating, in the presence of an initiator, preferably a free radical initiator, and optionally in the presence of one or more comonomers, at least one substituted phosphonylated 2,2′-dihydroxyl-1,1′-binaphthalene or at least one substituted 2,2′-dihydroxyl-1,1′-biphenylene.
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Page column 32
(2010/11/30)
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- PHOSPHONITE LIGANDS AND THEIR USE IN HYDROCYANATION
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Disclosed herein are processes for hydrocyanation and isomerization of olefins by using at least one multidentate phosphonite ligands, including organometallic phosphonite ligands with a Group VIII metal or Group VIII metal compound, and optionally, a Lewis acid promoter.
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Page/Page column 9-10
(2008/06/13)
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- Intramolecular titanium-mediated aminocyclopropanation of terminal alkenes: Easy access to various substituted azabicyclo[n.1.0]alkanes
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(Matrix presented) A variety of substituted azabicyclo[n.1.0]alkanes were synthesized by intramolecular titanium-mediated cyclopropanation of N-benzyl-N-(2-alkylalk-3-enyl)formamides and N-benzyl-N-alkadienylformamides. N-Benzylpyrroline upon treatment with Grignard reagents undergoes a titanium-mediated carbomagnesiation to yield N-benzyl-N-(2-alkylbut-3-enyl)amines.
- Tebben, Gerd-Dieter,Rauch, Karsten,Stratmann, Christian,Williams, Craig M.,De Meijere, Armin
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p. 483 - 485
(2007/10/03)
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- Transition Metal-Catalyzed Intramolecular Cyclization of 1,5- And 1,6-Dienes via Direct Cleavage and Addition of the Carbon-Hydrogen Bond
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Ruthenium- and rhodium-catalyzed intramolecular C-H/olefin coupling reactions of 1-(2-pyridyl)-, 1-(2-imidazolyl-, and 1-(2-oxazolyl)-1,5-dienes proceeded in a regiospecific manner to give 5-membered ring products. Their 1,6-diene analogues are also applicable to the cyclization reaction to give the corresponding 5- and 6-membered carbocycles. For the cyclization of the pyridine derivatives, [RhCl(PPh3)3] showed the highest catalytic activity with respect to efficiency and selectivity. When the imidazole derivatives were employed to the cyclization reaction, the combination of the rhodium(I) complex and the relatively sterically bulky phosphine (e.g., PCy3 and PPFOMe) was a quite effective catalyst system. In the case of the oxazoles, the ruthenium complex, [Ru(H)2(CO)(PPh3)3], showed the highest activity among the catalysts examined. These catalytic reactions usually proceed at 120°C. The [RhCl(PPh3)3]-catalyzed cyclization reaction of 2-[(1E)-4,4-dimethyl-1,5-hexadienyl]pyridine smoothly proceeded even at room temperature to give the corresponding cyclized product in 93% yield after 24 h. A hybrid catalyst system containing the rhodium(I) and both PPh3 and P(o-tolyl)3 had a slightly better catalytic activity compared with that of [RhCl(PPh3)3]. The intramolecular cyclization can be also applied to the C-H/CO/olefin coupling reactions. These carbonylation reactions gave the 5-membered ring ketones exclusively. The intramolecular C-H/olefin coupling reactions provide a new entry for constructing carbocyclic compounds from 1,n-dienes.
- Fujii, Naoaki,Kakiuchi, Fumitoshi,Yamada, Airi,Chatani, Naoto,Murai, Shinji
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p. 285 - 298
(2007/10/03)
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- Indane-2-mercaptoacetylamide disulfide derivatives useful as inhibitors of enkephalinase
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The present invention relates to certain novel indane-2-mercaptoacetylamide disulfide derivatives of the formula STR1 useful as inhibitors of enkephalinase.
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- 2-substituted indane-2-mercaptoacetylamide tricyclic derivatives useful as inhibitors of enkephalinase
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The present invention relates to novel 2-substitited indane-2-mercaptoacetylamide tricyclic derivatives which are useful as inhibitors of Enkephalise.
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- Mercaptoacetylamide tricyclic derivatives useful as inhibitors of enkephalinase
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The present invention relates to novel mercaptoacetylamide tricyclic derivatives useful as inhibitors of enkephalinase.
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- Cyclization of Alkoxyiminyl Radicals onto Olefins: Formation of 2-Alkoxy-Δ1-pyrrolines, 4,5-Dihydrooxazoles and 5,6-Dihydro-4H-1,3-oxazines
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Alkoxyiminyl radicals, generated by photolysis of N-bromo imidates, undergo exo-1,5 and exo-1,6 cyclization onto olefins on the O-alkyl side chain giving good yields of 4,5-dihydrooxazoles and 5,6-dihydro-4H-1,3-oxazines, respectively. exo-1,5 Cyclization onto an olefin on the iminyl side chain gives 2-alkoxy-Δ1-pyrrolines. 4,5-Dihydrooxazole formation is more favourable than cyclization to 2-alkoxy-Δ1-pyrrolines and both reactions are irreversible.These preferences are supported by MNDO molecular orbital calculations which predict that both processes are exotermic but cyclization onto the O-alkenyl side chain has a lower ΔH(excit.).
- Glover, Stephen A.,Hammond, Gerard P.,Harman, David G.,Mills, John G.,Rowbottom, Colleen A.
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p. 1213 - 1228
(2007/10/02)
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- Allyltris(trimethylsilyl)silane as Radical Allylating Agent for Organic Halides
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Reaction of allyltris(trimethylsilyl)silane with organic halides under the free radical conditions resulted in allylation of the halides in moderate to good yields.The presence of three trimethylsilyl groups on the silicon could enhance the homolytic dissociation of a Si-C bond in the β-silylalkyl radical.
- Kosugi, Masanori,Kurata, Hiroshi,Kawata, Ken-ichi,Migita, Toshihiko
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p. 1327 - 1328
(2007/10/02)
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- SIMPLE SYNTHESIS OF γ-LACTONES FROM OLEFINIC NITRILES
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The reaction of substituted 4-pentenonitriles with 50 percent sulphuric acid at 100 deg C afforded γ-lactones in moderate to good yield.
- Tiecco, Marcello,Tingoli, Marco,Testaferri, Lorenzo,Bartoli, Donatella
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p. 2817 - 2824
(2007/10/02)
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- Assessment of the Cyano Substituent Effect in the Inhibited Pyrolysis Kinetics of ω-Bromonitriles in the Gas Phase
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The kinetics of the gas-phase pyrolysis of several bromonitriles were determined in a static system over the temperature range of 389.7-470.1 deg C and the pressure range of 38.5-139 Torr.The reactions in seasoned vessels, and in the presence of at least a 4-fold excess of the free-radical inhibitor propene and/or toluene, are homogeneous and unimolecular and follow a first-order rate law.The rate coefficients are given by the following Arrhenius equations: for 3-bromopropionitrile, log k1(s-1) = (13.56+/-0.44)-(231.9+/-6.0)kJmol-1 (2.303RT)-1; for 4-bromobutyronitrile, log k1(s-1) = (14.12*/-0.33) -(233.5+/-4.5)kJmol-1 (2.303RT)-1; for 5-bromovaleronitrile, log k1(s-1) = (13.79+/-0.19)-(225.7+/-2.6)kJmol-1(2.303RT)-1.The electron-withdrawing effect of the CN group along the carbon chain deactivates the HBr elimination during pyrolysis.A plot of the log krel of the cyano substituents in ω-bromonitriles against ?* values gives a good straight line with ρ* = -0.24, correlation coefficient r = 0.988, and intercept = -0.054 at 400 deg C.This slope inflects at ?*(CH3) = 0.00 with another good straight line derived by plotting the log krel vs ?* values of alkyl β-substituted ethyl bromides (? = -1.87, r = 0.991, and intercept = 0.056 at 400 deg C).The present result is explained in terms of slight alteration in the polarity of the transition state due to changes of electronic transmission at the carbon reaction center.
- Chuchani, Gabriel,Dominguez, Rosa M.
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p. 203 - 205
(2007/10/02)
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- IODINE-INDUCED IMINOTHIOLACTONIZATION OF γ,δ-UNSATURATED SECONDARY THIOAMIDES, NEW ENTRY TO 2-ACETOAMIDOTHIOPHENES
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Iodine-induced cyclization of γ,δ-unsaturated secondary thioamides 1 proceeded regio- (5-exo-trigonal) and chemo- (sulfur-carbon bond formation)selectively, providing iminothiolactones 2, which were converted in two-step sequences (dehydroiodination and N-acetylation) into 2-acetoamidothiophenes 4.This procedure was performed in one flask to afford polysubstituted 2-aminothiophenes.
- Takahata, Hiroki,Suzuki, Toshiaki,Maruyama, Mihoko,Moriyama, Keiko,Mozumi, Mayumi,et.al.
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p. 4777 - 4786
(2007/10/02)
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- Trifluoroacetoxysulphenylation of Unsaturated Nitriles and Transformation of the Adducts into Lactones
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Reactions of metal acetates with organic disulphides in dichloromethane-trifluoroacetic acid in the presence of unsaturated nitriles give trifluoroacetoxy sulphides, which on hydrolysis readily afford mixtures of the regioisomeric hydroxy sulphides.Optimum yields were obtained with manganese(III)acetate.The mixtures of regioisomeric trifluoroacetoxy sulphides react with acetonitrile under Ritter conditions to give further mixtures of regioisomeric vicinal acetamido sulphides.The regiochemistry of these reactions is discussed.Hydrolysis of the mixtures of trifluoroacetoxy sulphides in aqueous cobalt chloride gives substituted lactones.This high-yield transformation depends upon lactonisation proceeding via an episulphonium ion intermediate; hence conversion of unsaturated nitriles into sulphenyl lactones is characterised by good regiocontrol.
- Samii, Zakaria K. M. Abd El,Ashmawy, Mohamed I. Al,Mellor, John M.
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p. 2523 - 2532
(2007/10/02)
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- Elimination and Addition Reactions. Part 41. Nucleophilic Eliminative Fission of Cyclopropanes: the Coiled Spring Effect of Ring Strain on Nucleofugality and its Evaluation
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Rates have been measured of sulphonyl-activated eliminative ring fissions of a series of six cyclopropanes in which the leaving group is stabilised by alkoxycarbonyl, cyano, or sulphonyl groups.The measurements allow assignment of ranks (nucleofugalities) to carbon leaving groups in systems in which the connection to the leaving group is strained by incorporation in a cyclopropane ring.The values obtained are compered with those obtained for a unstrained (acyclic) analogues.Rank enhancements of about 9(log) units are obtained; these enhancements suggests that free energies of activation for leaving-group expulsion are reduced by about 53 kJmol-1, or about 46 percent of these excess of enthalpy of the strained ring, notwithstanding the small degree of ring fission in the transition structure.The effect of phenyl substitution at the leaving group suggests that cleavage of the ring is very little advanced in the transition structure, although this is variable with the nature of the leaving-group stabilisation.This is the first direct determination of the effect of strain on nucleofugality.
- Hughes, Simon,Griffiths, Gwerydd,Stirling, Charles J. M.
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p. 1253 - 1264
(2007/10/02)
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- TRIFLUOROACETOXYSULPHENYLATION OF UNSATURATED NITRILES AS A ROUTE TO LACTONES
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Use of manganic acetate as oxidant permits efficient trifluoroacetoxysulphenylation of unsaturated nitriles with organic disulphides.The adducts in a cobaltous chloride promoted hydrolysis afford alkyl- or aryl-thio substituted lactones.
- Samii, Zakaria K M Abd El,Ashmawy, Mohamed I Al,Mellor, John M
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p. 5293 - 5296
(2007/10/02)
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