- Copper-Catalyzed Cross-Nucleophile Coupling of β-Allenyl Silanes with Tertiary C-H Bonds: A Radical Approach to Branched 1,3-Dienes
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Described herein is a distinctive approach to branched 1,3-dienes through oxidative coupling of two nucleophilic substrates, β-allenyl silanes, and hydrocarbons appending latent functionality by copper catalysis. Notably, C(sp3)-H dienylation proceeded in a regiospecific manner, even in the presence of competitive C-H bonds that are capable of occurring hydrogen atom transfer process, such as those located at benzylic and other tertiary sites, or adjacent to an oxygen atom. Control experiments support the intermediacy of functionalized alkyl radicals.
- Shan, Qi-Chao,Hu, Lu-Min,Qin, Wei,Hu, Xu-Hong
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supporting information
p. 6041 - 6045
(2021/08/03)
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- Corresponding amine nitrile and method of manufacturing thereof (by machine translation)
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The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
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Paragraph 0136; 0137; 0142
(2018/07/15)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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Paragraph 0137; 0138; 0139; 0142; 0143
(2018/07/15)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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Paragraph 0136; 0137; 0140; 0142
(2018/05/24)
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- 2 - methyl malonic acid diester synthetic method of the compound
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The invention discloses a synthetic method of 2-diester methylmalonate compounds, and relates to the technical field of carboxylic ester preparation. The synthetic method comprises steps as follows: C, sulfonic acid 2-ethyl N-cyanoethanimideate IV and cyanide react under the action of a solvent and a catalyst, and 2-methyl malononitrile V is obtained; D, 2-methyl malononitrile V and ROH react under the action of the solvent and concentrated sulfuric acid, and products of 2-diester methylmalonate compounds I are obtained, wherein MCN is cyanide, M is Na or K, ROH is alkyl alcohol, alkenyl alcohol or a fluoride group containing alcohol, is benzyl alcohol or benzyl alkyl, halogen or nitro substituted benzyl alcohol, or is phenol or C1-C5 containing alkyl, halogen or nitro substituted phenol. The method is unique, the reaction conditions are mild, the reaction process is basically free of by-products, the yield is high, adopted raw materials have extensive sources, and acetaldehyde can be used as the raw material; the synthetic method is applicable to industrial production.
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Paragraph 0040-0041
(2017/08/10)
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- AlCl3 catalyzed coupling of: N-benzylic sulfonamides with 2-substituted cyanoacetates through carbon-nitrogen bond cleavage
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A new cross-coupling reaction of N-benzylic sulfonamides with 2-substituted cyanoacetates for the synthesis of 2-substituted benzylbenzene was reported. In the presence of AlCl3, a broad range of N-benzylic sulfonamides reacted smoothly with 2-substituted cyanoacetates to afford structurally diverse benzylbenzenes in moderate to excellent yields. The conversion could be enlarged to gram-scale efficiently. The practicability of this approach was further manifested in the synthesis of a related bioactive agent with high anti-inflammatory activity.
- Hu, Chen,Hong, Gang,Qian, Xiaofei,Kim, Kwang Rim,Zhu, Xiaoyan,Wang, Limin
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supporting information
p. 4984 - 4991
(2017/07/10)
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- Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation
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A new strategy for the functionalization of sterically hindered terminal olefins is reported. Alkenes bearing quaternary carbons at the allylic or homoallylic position are readily oxidized to the corresponding aldehydes by palladium/copper/nitrite catalysis. A broad range of functional groups including esters, nitriles, silyl ethers, vinylogous esters, ketones, lactones, and β-ketoesters are tolerated under the reaction conditions. The crude aldehyde products can be transformed further, enabling direct conversion of hindered terminal alkenes to various other synthetically useful functional groups, resulting in formal anti-Markovnikov hydroamination, among other transformations.
- Kim, Kelly E.,Li, Jiaming,Grubbs, Robert H.,Stoltz, Brian M.
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supporting information
p. 13179 - 13182
(2016/10/22)
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- A route to highly functionalized-enaminoesters via a domino ring-opening cyclization/decarboxylative tautomerization sequence of donor-acceptor cyclopropanes with substituted malononitriles
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An unprecedented and domino synthetic strategy for the synthesis of highly functionalized carbocyclic-enaminoesters bearing an all-carbon quaternary center via Yb(OTf)3-catalyzed ring-opening cyclization/decarboxylative tautomerization of donor-acceptor cyclopropanes with 2-alkyl malononitriles in excellent yields is described. The products are obtained as a single diastereomer in most cases where the nitrile and aryl groups are aligning in a cis orientation across the ring.
- Ghorai, Manas K.,Talukdar, Ranadeep,Tiwari, Deo Prakash
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supporting information
p. 2204 - 2207
(2014/05/06)
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- NOVEL TARGETING AGENTS FOR DIAGNOSTIC AND THERAPEUTIC INDICATIONS
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The invention relates to compounds and use thereof in the diagnosis and/or in treatment of medical disorders. In some embodiments, the compounds may be used for detecting a cancer. The compound may include a di-acid moiety. In some embodiments the di-acid moiety comprises a di-carboxylic acid and in some embodiments the di- acid moiety comprises a di-tetrazole.
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Paragraph 00156
(2013/10/22)
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- Tetrapodal amidoxime ligands I. Coordination isomerism due to self-complementary dimerization of a pyramidal cobalt(iii) coordination module
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A bis-μ-amidoximato-bridged cobalt(iii) dimer obtained with a new tetrapodal ligand possesses interesting structural parameters as a consequence of intramolecular hydrogen bonding intentionally built into the complex. Its synthesis and properties are described. The new ligand type combines attributes of two previously described ligand classes: It binds a metal ion in a tetrapodal pentadentate fashion and forms a pseudomacrocycle through hydrogen bonds, characteristic of chelating oxime ligands. Coordination isomerism, which is a consequence of dimer formation, has been analyzed by means of X-ray crystallography and carbon-13 nuclear magnetic resonance spectroscopy. The Royal Society of Chemistry 2012.
- Boyd, John P.,Irran, Elisabeth,Grohmann, Andreas
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experimental part
p. 2477 - 2485
(2012/03/22)
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- Charge-transfer interactions: An efficient tool for recycling bis(oxazoline)-copper complexes in asymmetric henry reactions
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An anthracenyl-modified chiral bis(oxazoline) copper complex has been demonstrated to efficiently promote nitroaldol reactions between structurally varying aldehydes and nitromethane or nitroethane. The catalyst was recovered through formation of a charge transfer complex between the chiral ligand and trinitrofluorenone and its subsequent precipitation with pentane. The efficiency of this procedure was proved through several consecutive catalytic cycles that allowed the sturdy formation of the expected product with a high enantioselectivity. The catalyst′s stability was also put to the test in an original multi-substrate procedure. Following the same recovery concept, a new heterogeneous procedure was tested for which trinitrofluorenone was covalently linked to a silica support. Asymmetric heterogeneous catalysis was performed under these conditions as one of the few examples demonstrating the potential catalyst recycling in nitroaldol reactions through reversible, non-covalent interactions. Copyright
- Didier, Dorian,Magnier-Bouvier, Caroline,Schulz, Emmanuelle
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supporting information; experimental part
p. 1087 - 1095
(2011/07/09)
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- SULFONYLPYRAZOLE AND SULFONYLPYRAZOLINE CARBOXAMIDINE DERIVATIVES AS 5-HT6 ANTAGONISTS
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This invention concerns sulfonylpyrazoline carboxamidine derivatives as antagonists of 5-HT6 receptors, to methods for the preparation of these compounds and to novel intermediates useful for their synthesis. The invention also relates to the uses of such compounds and compositions, particularly their use in administering them to patients to achieve a therapeutic effect in Parkinson's disease, Huntington's chorea, schizophrenia, anxiety, depression, manic depression, psychoses, epilepsy, obsessive compulsive disorders, mood disorders, migraine, Alzheimer's disease, age related cognitive decline, mild cognitive impairment, sleep disorders, eating disorders, anorexia, bulimia, binge eating disorders, panic attacks, akathisia, attention deficit hyperactivity disorder, attention deficit disorder, withdrawal from abuse of cocaine, ethanol, nicotine or benzodiazepines, pain, disorders associated with spinal trauma or head injury, hydrocephalus, functional bowel disorder, Irritable Bowel Syndrome, obesity and type-2 diabetes. The compounds have the general formula (1), wherein the symbols have the meanings given in the description.
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Page/Page column 38-39
(2008/06/13)
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- MALONONITRILE COMPOUND AND USE THEREOF AS PESTICIDES
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The present invention relates to a novel malononitrile compound represented by the formula (A): wherein, R1 represents C1 to C6 alkyl that may be substituted with halogen, C2 to C6 alkenyl that may be substituted with halogen, etc; R2 represents hydrogen atom or C1 to C6 alkyl that may be substituted with halogen; R3 represents hydrogen atom or C1 to C6 alkyl; R4 represents hydrogen atom or C1 to C6 alkyl; R5 represents C1 to C6 alkyl that may be substituted with halogen, C3 to C6 alkenyl that may be substituted with halogen, etc , or R4 and R5 may be combined at their terminal and represent ethylene that may be substituted with C1 to C3 alkyl or trimethylene that may be substituted with C1 to C3 alkyl; and Z1 and Z2, which are the same or different, represent oxygen atom or sulfur atom. The malononitrile compound has an efficient pesticidal activity and can control effectively pests such as insect pests, acarine pests, nematode pests and the like.
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- Carbopalladation of nitriles: Synthesis of benzocyclic ketones and cyclopentenones via Pd-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles and related compounds
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An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)-propanenitriles affords indanones in high yields. The reaction is compatible with a wide variety of functional groups. This methodology has been extended to the synthesis of tetralones and cyclopentenones.
- Pletnev, Alexandre A.,Larock, Richard C.
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p. 9428 - 9438
(2007/10/03)
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- Radical reaction initiated and stereocontrolled by zinc chloride
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The reaction of allyltributyltin with methyl 2-[N-((4S)-4-(1-methylethyl)-2-oxazolidinone-3-carbamoyl)amino]-2-bromoacetate (5 a) was accelerated at -50°C in the presence of AIBN and stopped in the presence of galvinoxyl, indicating that the reaction proceeds through a radical mechanism. The reaction was accelerated dramatically at -78°C in the presence of ZnCl2·OEt2, and the ZnCl2-mediated reaction was stopped in the presence of galvinoxyl. In the presence of 2 equiv ZnCl2·OEt2, the reaction afforded methyl (2R)-2-[N-((4SH-(1-methylethyl)-2-oxazolidinone-3-carbamoyl)amino]-4-pentenoate {6a(R)} with high diastereoselectivity (93:7). Taken together, ZnCl2·OEt2 works as a radical initiator as well as chelating agent.
- Yamamoto, Yoshinori,Onuki, Setsuko,Yumoto, Masatoshi,Asao, Naoki
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p. 765 - 780
(2007/10/03)
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- Cephalosporin compounds
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The present invention relates to new cephalosporin compounds of the formula(I), pharmaceutically acceptable non-toxic salts thereof, and physiologically hydrolyzable esters and solvates thereof, which have potent and broad antibacterial activities STR1 wherein R1 is a C1?4 alkyl, C3?4 alkenyl, C3?4 alkynyl group, or --C(Ra)(Rb)CO2 H1 wherein Ra and Rb are the same or different, and each is a hydrogen atom or a C1?4 alkyl group, or Ra and Rb form a C3?7 cycloalkyl group with the carbon atom to which they are linked; R2 is a C1?4 alkyl, C3?4 alkenyl or C3?4 cycloalkyl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted phenyl group; R3 is hydrogen or a C1?4 alkyl group; and Q is N or CH. The invention further relates to a process for preparing said compounds, and to pharamaceutical compositions containing said compounds.
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- Resonanzstabilisierung von Alkylradikalen durch zwei geminale Cyangruppen
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Effects of Substituents on the Strength of C-C bonds, 10. - Resonance Stabilization of Alkyl Radicals by Two Geminal Cyano groups The activation parameters of the homolytic cleavage of the Cq-Cq bonds of several dialkylated malonodinitriles (2-5) and of 1,1,2,2-tetracyanoethane (7) and the heat of dissociation of 6 in solution have been determined.Together with the ground state strain of the radical precursor (obtained from the heats of combustion or EFF calculations) the steric influence on the dissociation process has been determined.The resonancestabilization energy of α,α'-dicyanoalkyl radicals then calculated was (12.4 +/- 0.9) kcal/mol.This result is discussed within the concept of capto-dative stabilization.The destabilizing interaction of two geminal cyano groups is apparently the same in the ground state of 2-7 and the radicals generated from them.
- Pakusch, Joachim,Beckhaus, Hans-Dieter,Ruechardt, Christoph
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p. 1191 - 1198
(2007/10/02)
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- Phase Transfer Catalysis without Solvent: Selective Mono- or Di-alkylation of Malononitrile
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Monoalkyl and symmetrical or unsymmetrical dialkylmalononitriles have been prepared selectively by phase transfer catalysis in the absence of solvent.Exclusive formation of a particular compound is achieved in all cases except for benzylmalononitrile 2f (79percent) and prop-2-ynylmalononitrile 2g (62percent).
- Diez-Barra, Enrique,Hoz, Antonio de la,Moreno, Andres,Sanchez-Verdu, Prado
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p. 2589 - 2592
(2007/10/02)
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- Chemistry of alpha-aminonitriles. Aziridine-2-carbonitrile: photochemical formation from 2-aminopropenenitrile
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2-Aminopropenenitrile in solvents such as MeCN, MeOH, or H2O is photoisomerized by UV light to racemic aziridine-2-carbonitrile (rac-2); the larger part of the starting material, however, fragments to HCN and MeCN. The observed photocyclization constitutes a structural connection within an ensemble of C3H4N2 compounds considered to be potentially relevant to prebiotic chemistry.
- Drenkard,Ferris,Eschenmoser
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p. 1373 - 1390
(2007/10/02)
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- Ruthenium-catalyzed Reductive Alkylation of Active Methylene Compounds with Aldehydes under Synthesis Gas
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Active methylene compounds undergo reductive alkylation with aldehydes when heated at 135-230 deg C under synthesis gas of 100 atm in the presence of ruthenium carbonyl.
- Abe, Fujio,Hayashi, Teruyuki,Tanaka, Masato
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p. 765 - 768
(2007/10/02)
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