- Binaphthol-based diphosphite ligands in asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene: Influence of steric properties
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A series of chiral (R)-binaphthol-based diphosphite ligands with different substituents was prepared and applied in the asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene to investigate the influence of their steric properties. The optimum steric properties for the hydrocyanation reaction lie within a narrow window. With the optimized ligand, hydrocyanation of styrene gave full conversion (Subs/Ni = 100) with 49% ee, the TON was determined to be 600. Hydrocyanation of 1,3-cyclohexadiene gave 50% conversion (Subs/Ni = 500) with an excellent ee of 86 %. This demonstrates that high ees are not only accessible for vinylarenes but also for conjugated dienes in the asymmetric nickelcatalyzed hydrocyanation.
- Wilting, Jos,Janssen, Michele,Mueller, Christian,Lutz, Martin,Spek, Anthony L.,Vogt, Dieter
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- Solvent-free Diels-Alder reaction in a closed batch system
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Solvent-free Diels-Alder reactions were carried out by heating a mixture of a volatile diene, such as 1,3-butadiene, isoprene, or 2,3-dimethyl-1,3- butadiene, and a dienophile, such as methyl vinyl ketone, methyl acrylate, or maleic anhydride, in a closed batch reactor. High yields of Diels-Alder products were obtained without using solvents and catalysts within a short reaction time in most of the reactions. In particular, several reactions of dienophiles with 1,3-butadiene, which is known as a diene with low reactivity because of its gaseous form, also proceeded with high yields of Diels-Alder products in the closed batch reactor under conditions pressured by the reactant vapor. Solvent-free reactions provided high yields compared to reactions in solvent since the reaction heat directly resulted in increasing the reaction temperature and pressure. Energy in the exothermic reaction was used effectively in the closed batch system under solvent-free conditions.
- Sun, Daolai,Sato, Fumiya,Yamada, Yasuhiro,Sato, Satoshi
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- NEW LEWIS ACID CATALYSTS FOR THE DIELS-ALDER REACTION
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Catechol boron bromide (1) and ferrocenium hexafluorophosphate (2) function as Lewis acid catalysts for the Diels-Alder reaction.
- Kelly, T. Ross,Maity, Sanat K.,Meghani, Premji,Chandrakumar, Nizal S.
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- OXIDATIVE CONVERSION OF ALIPHATIC ALDEHYDES TO NITRILES USING OXOAMMONIUM SALT
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The present invention relates to an oxidative transformation method of aliphatic benzaldehydes to nitriles using NH_4OAc through oxoammonium salts. By using stoichiometric amounts of oxoammonium salts to establish optimal reaction conditions associated with the oxidative conversion of aliphatic benzaldehydes to nitriles, high yields of nitrile can be selectively obtained, and the oxoammonium salts used can be oxidized and reused in a simple method.COPYRIGHT KIPO 2020
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Paragraph 0055-0063; 0136-0142
(2019/12/10)
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- Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate
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An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH4OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.
- Kim, Myeong Jin,Mun, Junyoung,Kim, Jinho
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supporting information
p. 4695 - 4698
(2017/11/17)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0143-0145; 0149; 0160; 0182; 0193; 0215; 0226
(2017/10/22)
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- Cyanide-Free and Broadly Applicable Enantioselective Synthetic Platform for Chiral Nitriles through a Biocatalytic Approach
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A cyanide-free platform technology for the synthesis of chiral nitriles by biocatalytic enantioselective dehydration of a wide range of aldoximes is reported. The nitriles were obtained with high enantiomeric excess of >90 % ee (and up to 99 % ee) in many cases, and a “privileged substrate structure” with respect to high enantioselectivity was identified. Furthermore, a surprising phenomenon was observed for the enantiospecificity that is usually not observed in enzyme catalysis. Depending on whether the E or Z isomer of the racemic aldoxime substrate was employed, one or the other enantiomer of the corresponding nitrile was formed preferentially with the same enzyme.
- Betke, Tobias,Rommelmann, Philipp,Oike, Keiko,Asano, Yasuhisa,Gr?ger, Harald
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supporting information
p. 12361 - 12366
(2017/09/06)
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- Acetohydroxamic acid: A new reagent for efficient synthesis of nitriles directly from aldehydes using Bi(OTf)3 as the catalyst
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An efficient method for the preparation of nitriles directly from aldehydes by reaction with AHA using Bi(OTf)3 as the catalyst is described. Bi(OTf)3 is shown to be an efficient catalyst also for the conversion of aldoximes into nitriles.
- Sridhar, Madabhushi,Reddy, Mallu Kishore Kumar,Sairam, Vangipuram Venkata,Raveendra, Jillella,Godala, Kondal Reddy,Narsaiah, Chinthala,Ramanaiah, Beeram China,Reddy, Cirandur Suresh
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experimental part
p. 3421 - 3424
(2012/08/08)
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- PROCESS FOR PREPARING CYCLIC DIAMINES
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The present invention relates to a process for preparing a cyclic diamine, comprising the reaction of at least one cyclic alkene with a gas mixture (G) comprising dinitrogen monoxide to give at least one cyclic ketone and the subsequent conversion of the
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Page/Page column 25-26
(2010/06/15)
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- Synthetic studies related to diketopyrrolopyrrole (DPP) pigments. Part 1: The search for alkenyl-DPPs. Unsaturated nitriles in standard DPP syntheses: A novel cyclopenta[c]pyrrolone chromophore
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Reactions of the anion of ethyl 4,5-dihydro-5-oxo-2-phenylpyrrole-3-carboxylate with the Diels-Alder adducts of acrylonitrile and various dienes rarely yield the expected DPP derivatives. The reaction with cyclohex-3-enecarbonitrile provides a noteworthy exception: thermolysis of the resulting cyclohexenyl-DPP gives butadiene and impure 3-ethenyl-6-phenyl-DPP, the latter being thermally unstable. Michael additions predominate when the above anion reacts with α,β-unsaturated nitriles: acrylonitrile and methacrylonitrile give 4,4-bis(cyanoethyl) and 4,4-bis(2-cyanopropyl) derivatives, and cinnamonitrile, substituted cinnamonitriles and 3-(2-thienyl)acrylonitrile give deep red 3-aryl-5-cyano-4-hydroxy-2H-cyclopenta[c]pyrrol-1-ones. These ambident nucleophiles may undergo N- and either O- or C-alkylation according to the alkylating agent used.
- Morton, Colin J.H,Gilmour, Ryan,Smith, David M,Lightfoot, Philip,Slawin, Alexandra M.Z,MacLean, Elizabeth J
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p. 5547 - 5565
(2007/10/03)
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- Diels-Alder reactions using supercritical water as an aqueous solvent medium
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A variety of Diels-Alder reactions have been performed in supercritical water as a reaction medium. The rapid reaction of Diels-Alder reactions of cyclopentadiene and various electron poor dienophiles such as diethyl fumarate and acrylonitrile is observed in supercritical water, and leads to high yields of clean products without added catalysts.
- Korzenski, Michael B.,Kolis, Joseph W.
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p. 5611 - 5614
(2007/10/03)
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- Diene Oligomerization. XV. Palladiumcomplexcatalyzed Telomerization of Butadiene with Amines and Dimerization in the Presence of Ketoximes
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Butadiene reacts with primary or secondary amines and with the homogeneous catalytic system bis-acetylacetonatopalladium-(II)/triphenylphosphine to form 1-amino-octa-2,7-dienes.The rate and the selectivity of the reaction increase in presence of cocatalysts as triarylphosphates instead of triphenylphosphine and if the reaction proceeds in a protic media - in alcohols, water or lower carboxylic acids.A number of 1-aminoocta-2,7-dienes were prepared.If oximes act as organic nitrogen compounds, only n-octa-1,3,7-triene is selectively formed.Schiff' bases aldolisate under the conditions of the reaction.
- Beger, J.,Meier, F.
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