- Reversal of aryl bromide reactivity in Pd-catalysed aryl amination reactions promoted by a hemilabile aminophosphine ligand
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Incorporation of a hemilabile amino group with a bulky, electron-rich phosphorus ligand led to a reversal in the order of aryl bromide reactivity in Pd-catalysed aryl amination reactions.
- Parisel, Sebastien L.,Adrio, Luis Angel,Pereira, Adriana Amoedo,Pérez, Marta Marino,Vila, José M.,Hii, King Kuok
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Read Online
- Al(OTf)3-Catalyzed Tandem Coupling Reaction between N,N-Disubstituted Aminomalonitriles and Substituted Arenes: a Synthesis of 1-Cyano-bisindolylmethane Analogues≠
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A synthesis of 1-cyano-bisindolylmethane analogues via an Al(OTf)3-catalyzed tandem coupling reaction between N,N-disubstituted aminomalonitriles and substituted arenes has been developed. This method not only provides an alternative synthetic strategy for the synthesis of corresponding functional molecules, but also enriches the volume of bisarylmethanes library to facilitate related functional studies. (Figure presented.).
- Lei, Lin-Sheng,Wang, Bo-Wen,Jin, Da-Ping,Gao, Zhu-Peng,Huan-Liang,Wang, Shao-Hua,Xu, Xue-Tao,Zhang, Kun,Zhang, Xiao-Yun
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Read Online
- KINASE INHIBITOR
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The present invention aims to provide a novel kinase inhibitor and the like, and a therapeutic agent for a disease, a drug discovery screening method and the like utilizing such inhibitor and the like. The compound represented by the following formula (I) and a salt thereof can inhibit plural kinases including LATS (particularly LATS2) which is the major kinase in the Hippo signal transduction pathway. In addition, diseases or tissue damage associated with failure of cellular proliferation can be treated. Therefore, the present invention is beneficial, for example, in the research field of cell functions and diseases, in which the Hippo signal transduction pathway is involved, and the like. Furthermore, it is beneficial in the medical field for the treatment of such diseases and the like. wherein each symbol is as defined in the DESCRIPTION.
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Paragraph 0221; 0222
(2021/04/16)
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- Photoredox-Catalyzed α-Aminomethyl Carboxylation of Styrenes with Sodium Glycinates: Synthesis of γ-Amino Acids and γ-Lactams
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A visible-light photoredox-catalyzed reductive α-aminomethyl carboxylation of styrenes with sodium glycinates and CO2 has been developed to synthesize a series of α,α-disubstituted γ-amino acids and γ-lactams with high efficiency and regioselectivity. Notably, CO2 released from the decarboxylation step can be reused for the subsequent carboxylation. Distinct from the previous reactions with the same type of substrates leading to simple decarboxylation and olefin hydroalkylation, this process involves additional CO2 sequestration, thus leading to olefin α-aminomethyl carboxylation. These findings not only provide new access to α,α-disubstituted γ-amino acids and γ-lactams but also serve as a proof of concept for CO2 reutilization in decarboxylation reactions.
- Zhou, Cong,Li, Miao,Sun, Jianwei,Cheng, Jiang,Sun, Song
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supporting information
p. 2895 - 2899
(2021/05/05)
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- Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents
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Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate (EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and aliphatic amines for the first time. It was revealed that the ruthenium octabutoxyphthalocyanine carbonyl complex [(BuO)8Pc]Ru(CO) is the most efficient catalyst converting electron-rich and electron-poor aromatic olefins to cyclopropane derivatives with high yields (typically 80-100%) and high TON (up to 1000) under low catalyst loading and nearly equimolar substrate/EDA ratio. This catalyst shows a rare efficiency in the carbene insertion into amine N-H bonds. Using a 0.05 mol% catalyst loading, a high amine concentration (1 M) and 1.1 eq. of EDA, a number of structurally divergent amines were selectively converted to mono-substituted glycine derivatives with up to quantitative yields and turnover numbers reaching 2000. High selectivity, large substrate scope, low catalyst loading and practical reaction conditions place [(BuO)8Pc]Ru(CO) among the most efficient catalysts for the carbene insertion into amines.
- Cailler, Lucie P.,Kroitor, Andrey P.,Martynov, Alexander G.,Gorbunova, Yulia G.,Sorokin, Alexander B.
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supporting information
p. 2023 - 2031
(2021/02/26)
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- ADDITIVE COMPOSITION FOR CULTURE MEDIUM, ADDITIVE COMPOUND FOR CULTURE MEDIUM, AND METHOD FOR CULTURE OF CELLS OR TISSUE USING SAME
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The present invention provides a medium additive composition containing a compound represented by the following formula (I), or a salt thereof: {wherein each symbol is as defined in the DESCRIPTION.}
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Paragraph 0211-0212
(2020/06/15)
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- Novel synthesis of aminoacetonitriles via the selective demethylation of quaternary ammonium salts
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N-Methyl cyclic amines readily formed quaternary ammonium salts upon treatment with iodoacetonitrile in high yields (70–96%). The latter were selectively demethylated by heating in dimethylformamide to give aminoacetonitriles in moderate to good overall y
- Buev, Evgeny M.,Smorodina, Anastasia A.,Stepanov, Maxim A.,Moshkin, Vladimir S.,Sosnovskikh, Vyacheslav Y.
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p. 1638 - 1641
(2018/04/02)
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- Method for synthesizing alpha-amino-acid ester compound through catalytic oxidation one-step process
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The invention belongs to the technical field of organic chemical industry and discloses a method for synthesizing an alpha-amino-acid ester compound through a catalytic oxidation one-step process. The method comprises the following steps: (1) reacting a vinyl ether/amine compound or alkene amide compound with an amine compound in an organic solvent under a synergic effect of a catalyst and an oxidizing agent; and (2) separating and purifying a product after the ending of the reaction, thereby acquiring the alpha-amino-acid ester compound. The method is simple and safe in operation, the compound is synthesized within one step, an ester bond is acquired in a reaction process, a nontoxic pollution-free peroxide is used as an oxidizing agent, the raw materials are low in cost and are easily acquired and the alpha-amino-acid ester compound has wide adaptability to functional groups, wide adaptability to substrates, environmental protection and an excellent industrial application prospect.
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Paragraph 0053; 0055; 0057; 0059; 0061; 0064; 0065; 0072
(2017/09/01)
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- Access to α-Amino Acid Esters through Palladium-Catalyzed Oxidative Amination of Vinyl Ethers with Hydrogen Peroxide as the Oxidant and Oxygen Source
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A novel and convenient palladium catalytic system for the synthesis of α-amino acid esters from simple starting materials is reported. Hydrogen peroxide not only acts as the green oxidant, but also as the oxygen source. This strategy for the conversion of amines and vinyl ethers into highly functionalized and structurally diverse α-amino acid esters is characterized by the simplicity of the experimental procedure, mild reaction conditions, high atom economy, scalability, and practicability.
- Ouyang, Lu,Li, Jianxiao,Zheng, Jia,Huang, Jiuzhong,Qi, Chaorong,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 15926 - 15930
(2017/11/23)
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- CURE ACCELERATORS FOR ANAEROBIC CURABLE COMPOSITIONS
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Cure accelerators for anaerobic curable compositions, such as adhesives and sealants, are provided, and which are defined with reference to the compounds shown in structure I where A is CH2 or benzyl, R is C1-10 alkyl, R′ is H or Cs
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Paragraph 0086; 0090
(2017/07/14)
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- Polymer-supported ruthenium(II)/phenyloxazoline complex: Reusable and highly selective catalyst for N-H insertion reactions
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A group of functionalized β-amino esters were successfully synthesized in excellent yields (> 99 %) via NH-insertion of ethyldiazoacetate into various amines catalyzed by porous-polymer-supported ruthenium(II)-pheox catalyst. The catalyst was readily recovered and reused at least five times without loss of its catalytic activity.
- Abu-Elfotoh, Abdel-Moneim
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p. 349 - 352
(2017/01/24)
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- NH insertion reactions catalyzed by reusable water-soluble ruthenium(II)-hm-phenyloxazoline complex
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A water-soluble Ru(II)-hm-pheox complex was efficiently catalyzed NH insertion of EDA with a broad class of amine derivatives in water/ether biphasic medium to deliver the biologically active precursors α-aminoester products with excellent yields (up to >99%). The products were separated by decantation and the catalyst was washed and reused several times (at least 8 times) without any specific loss of its catalytic activity. The plausible mechanism of the reaction was explained. Additionally, In case of ethylene diamine, the NH insertion product could be transformed to biological active piperazinone compound in high yield. The asymmetric version of this catalytic reaction is under investigation.
- Abu-Elfotoh, Abdel-Moneim
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supporting information
p. 4750 - 4754
(2017/11/29)
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- MYOGLOBIN-BASED CATALYSTS FOR CARBENE TRANSFER REACTIONS
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Methods are provided for carrying out carbene transfer transformations such as olefin cyclopropanation reactions, carbene heteroatom-H insertion reactions (heteroatom = N, S, Si), sigmatropic rearrangement reactions, and aldehyde olefination reactions with high efficiency and selectivity by using a novel class of myoglobin-based biocatalysts. These methods are useful for the synthesis of a variety of organic compounds which contain one or more new carbon-carbon or carbon-heteroatom (N, S, or Si) bond. The methods can be applied for conducting these transformations in vitro (i.e., using the biocatalyst in isolated form) and in vivo (i.e., using the biocatalyst in a whole cell system).
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Paragraph 00278; 00279; 00288
(2016/06/14)
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- Transition-metal-free decarboxylation of dimethyl malonate: An efficient construction of α-amino acid esters using TBAI/TBHP
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A transition-metal-free decarboxylation coupling process for the preparation of α-amino acid esters, which succeeded in merging hydrolysis/decarboxylation/nucleophilic substitution, is well described. This strategy uses commercially available inexpensive starting materials, catalysts and oxidants and has a wide substrate scope and operational simplicity. This journal is
- Zhang, Jie,Shao, Ying,Wang, Yaxiong,Li, Huihuang,Xu, Dongmei,Wan, Xiaobing
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p. 3982 - 3987
(2015/03/30)
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- Myoglobin-catalyzed intermolecular carbene N-H insertion with arylamine substrates
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Engineered variants of the heme-containing protein myoglobin can efficiently catalyze the insertion of α-diazo esters into the N-H bond of arylamines, featuring a combination of high chemoselectivity, elevated turnover numbers, and broad substrate scope.
- Sreenilayam, Gopeekrishnan,Fasan, Rudi
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supporting information
p. 1532 - 1534
(2015/08/03)
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- Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
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A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
- O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
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supporting information
p. 474 - 478
(2014/01/23)
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- PYRAZOLO[3,4-D]PYRIMIDIN-4(5H)-ONE DERIVATIVES AS PDE9 INHIBITORS
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A compound of the general formula (I) wherein R1 is selected from the group consisting of phenyl unsubstituted or substituted with 1 to 3 substituents selected from F, Cl, Br, I, CN, -O-C1-C3-alkyl, fluorinated -O-C1-C3-alkyl, -(CH2)mOH and 5-membered heterocyclic group with 1 or 2 heteroatoms selected from N, O and S; and 6- or 10-membered heteroaryl with 1 to 3 heteroatoms selected from O, N and S; R2 and R3 independently of each other represent H atom or straight or branched C1-C3 alkyl; R4 is selected from the group consisting of 4- to 6- membered cycloalkyl, wherein one of carbon atoms can be replaced by O atom, and which is unsubstituted or substituted with one or two halogen atoms,and straight or branched C1-C4 alkyl; Q represents a bond or C1-C3-alkylene, which can be optionally substituted by one to three C1-C3-alkyls; X is selected from the group consisting of O, NR5, and S(O)p; R5 represents H atom or C1-C3alkyl; m is 1, 2 or 3; p is 0, 1 or 2; and salts thereof, for use as a medicament, in particular for treating cognitive function disorders and neurodegenerative diseases.
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- Cytochrome P450-catalyzed insertion of carbenoids into N-H bonds
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Expanding nature's catalytic repertoire to include reactions important in synthetic chemistry will open new opportunities for 'green' chemistry and biosynthesis. We demonstrate the first enzyme-catalyzed insertion of carbenoids into N-H bonds. This type of bond disconnection, which has no counterpart in nature, can be mediated by variants of the cytochrome P450 from Bacillus megaterium. The N-H insertion reaction takes place in water, provides the desired products in 26-83% yield, forms the single addition product exclusively, and does not require slow addition of the diazo component.
- Wang, Z. Jane,Peck, Nicole E.,Renata, Hans,Arnold, Frances H.
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p. 598 - 601
(2014/01/17)
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- P-Tolylimido rhenium(v) complexes-synthesis, X-ray studies, spectroscopic characterization, DFT calculations and catalytic activity
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Novel p-tolylimido rhenium(v) complexes trans-(Cl,Cl)-[Re(p-NC 6H4CH3)Cl2(py-2-COO)(PPh 3)]·MeCN (1a), trans-(Cl,Cl)-[Re(p-NC6H 4CH3)Cl2(py-2-COO)(PPh3)] (1b), trans-(Br,Br)-[Re(p-NC6H4CH3)Br 2(py-2-COO)(PPh3)] (2), cis-(Cl,Cl)-[Re(p-NC 6H4CH3)Cl2(py-2-COO)(PPh 3)] (3), cis-(Br,Br)-[Re(p-NC6H4CH 3)Br2(py-2-COO)(PPh3)]·H2O (4), trans-(Cl,Cl)-[Re(p-NC6H4CH3)Cl 2(OMe)] (5) and trans-(Br,Br)-[Re(p-NC6H 4CH3)Br2(OMe)(PPh3) 2]·1/2H2O (6) were synthesized. The compounds were identified by elemental analysis, IR, NMR (1H, 13C and 31P), UV-Vis spectroscopy and X-ray crystallography. Calculations at the DFT level were undertaken in order to elucidate the structural, spectroscopic and bonding properties of the trans-(Cl,Cl) and cis-(Cl,Cl) isomers of [Re(p-NC6H4CH3)Cl 2(py-2-COO)(PPh3)]. In the first step, extended tests of the ability of different DFT methods (B3LYP, BP86, and PBE1PBE) were performed to find the best overall performer in describing the geometry of the imido Re(v) complexes; then, the electronic spectra of the trans and cis isomers of [Re(p-NC6H4CH3)Cl2(py-2-COO) (PPh3)] were investigated at the TDDFT level employing the PBE1PBE functional. Additional information about bonding in the compounds [Re(p-NC 6H4CH3)Cl2(py-2-COO)(PPh 3)] was obtained by NBO analysis. The catalytic activity of the complexes incorporating the picolinate ligand was studied and compared in the synthesis of N-substituted ethyl glycine esters from ethyl diazoacetate and amines.
- Machura, Barbara,Gryca, Izabela,Malecki, Jan Grzegorz,Alonso, Francisco,Moglie, Yanina
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p. 2596 - 2610
(2014/02/14)
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- Iron-catalyzed oxidative amidation of tertiary amines with aldehydes
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Unconventional couple: A new oxidative coupling protocol for amide bond formation has been developed (see scheme). The method provides an efficient and practical route for the synthesis of tertiary amides from readily available tertiary amines and aldehydes in the presence of a simple FeCl2 catalyst. Mechanistic studies indicated that a peroxide and an iminium ion act as the reactive intermediates in this oxidative amidation.
- Li, Yuanming,Jia, Fan,Li, Zhiping
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supporting information
p. 82 - 86
(2013/03/13)
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- A new strategy for the construction of α-amino acid esters via decarboxylation
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A new α-amino acid esters formation reaction has been developed via decarboxylation. The methodology is distinguished by its practical novelty in terms of the readily accessible starting materials, environmentally benign reaction conditions and waste streams, and wide substrate scope.
- Zhang, Jie,Jiang, Jiewen,Li, Yuling,Zhao, Yun,Wan, Xiaobing
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supporting information
p. 3222 - 3225
(2013/07/26)
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- Iridium porphyrin catalyzed N-H insertion reactions: Scope and mechanism
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Ir(TTP)CH3 catalyzed N-H insertion reactions between ethyl diazoacetate (EDA) or methyl phenyldiazoacetate (MPDA) and a variety of aryl, aliphatic, primary, and secondary amines to generate substituted glycine esters with modest to high yields. Aniline substrates generally gave yields above 80%, with up to 105 catalyst turnovers, and without slow addition of the diazo reagent. Good yields were also achieved with aliphatic amines, though higher catalyst loadings and slow addition of the amine were necessary in some cases. Primary amines reacted with EDA to generate both single- and double-insertion products, either of which could be produced selectively in high yield with the proper choice of stoichiometric ratios and reaction temperature. Notably, mixed trisubstituted amines, RN(CH2CO2Et) (CHPhCO2Me), were generated from the insertion of 1 equiv of EDA and 1 equiv of MPDA into primary amines. The N-H insertion mechanism was examined using substrate competition studies, trapping experiments, and multiple spectroscopic techniques. Substrate competition studies using pairs of amines with EDA or MPDA revealed Hammett correlations with respective slopes of ρ = 0.15 and ρ+ = -0.56 as well as kinetic isotope ratios of k H/kD = 1.0 ± 0.2 and 2.7 ± 0.2. Competitive amine binding to the iridium center was demonstrated by kinetics and equilibrium binding studies. Equilibrium binding constants ranged from 102 to 105. Monitoring the reaction by absorption spectroscopy revealed a transient metalloporphyrin complex. The lifetime of this species was dependent on the nature of the amine substrate, which suggests that the catalytic cycle proceeds through a metal-ylide intermediate.
- Anding, Bernie J.,Woo, L. Keith
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p. 2599 - 2607
(2013/06/26)
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- Copper(II)-acid co-catalyzed intermolecular substitution of electron-rich aromatics with diazoesters
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The intermolecular aromatic substitution of N,N-dialkylanilines and alkoxybenzenes with diazoesters is shown to proceed in the presence of catalytic amounts of both copper(II) salt and acid (Lewis or Br?nsted). This method is a mild and rare metal-free C-C bond formation reaction between aromatic (sp2) and aliphatic (sp3) carbons.
- Tayama, Eiji,Ishikawa, Moe,Iwamoto, Hajime,Hasegawa, Eietsu
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supporting information; experimental part
p. 5159 - 5161
(2012/10/07)
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- Ruthenium Catalysts and Uses Thereof
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Ruthenium nanoparticles supported on non-cross-linked soluble polystyrene were prepared by reacting [RuCl2(C6H5CO2Et)]2 with polystyrene in open air. They effectively catalyze intra- and intermolecular carbenoid insertion into C—H and N—H bonds, alkene cyclopropanation, and ammonium ylide/[2,3]-sigmatropic rearrangement reactions. This supported ruthenium catalyst is much more reactive than [RuCl2(p-cymene)]2 and Ru(Por)CO] for catalytic intermolecular carbenoid C—H bond insertion into saturated alkanes. By using a-diazoacetamide as a substrate for intramolecular carbenoid C—H insertion, the supported ruthenium catalyst can be to recovered and reused for ten successive iterations without significant loss of activity.
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Page/Page column 4; 9
(2011/02/15)
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- Copper(II) triflate catalyzed intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters
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The intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters is achieved under mild conditions in the presence of a catalytic amount of copper(II) triflate (up to 89 % yield). The scope and limitations regarding substrates, diazo esters, and ligands in this reaction are described. The intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters is shown to proceed under mild conditions in the presence of a catalytic amount of copper(II) triflate/ligand complex(up to 89 % yield). The scope and limitations regarding substrates, diazoesters, and ligands in this reaction are described. Copyright
- Tayama, Eiji,Yanaki, Tomoyo,Iwamoto, Hajime,Hasegawa, Eietsu
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supporting information; experimental part
p. 6719 - 6721
(2011/02/28)
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- Iron-catalyzed synthesis of glycine derivatives via carbon-nitrogen bond cleavage using diazoacetate
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Treatment of tertiary amines with diazoacetate in the presence of a catalytic amount of an iron salt, FeCl3, in ethanol gave glycine derivatives. In this reaction, a carbon-nitrogen single bond of the amine was cleaved. The Royal Society of Chemistry 2010.
- Kuninobu, Yoichiro,Nishi, Mitsumi,Takai, Kazuhiko
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supporting information; scheme or table
p. 8860 - 8862
(2011/02/28)
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- A water-soluble ruthenium glycosylated porphyrin catalyst for carbenoid transfer reactions in aqueous media with applications in bioconjugation reactions
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Water-soluble [RuII(4-Glc-TPP)(CO)] (1, 4-Glc-TPP ) = meso-tetrakis(4-(β-D-glucosyl)phenyl)porphyrinato dianion) is an active catalyst for the following carbenoid transfer reactions in aqueous media with good selectivities and up to 100% conversions: intermolecular cyclopropanation of styrenes (up to 76% yield), intramolecular cyclopropanation of an allylic diazoacetate (68% yield), intramolecular ammonium/ sulfonium ylide formation/[2,3]-sigmatroptic rearrangement reactions (up to 91% yield), and intermolecular carbenoid insertion into N-H bonds of primary arylamines (up to 83% yield). This ruthenium glycosylated porphyrin complex can selectively catalyze alkylation of the N-terminus of peptides (8 examples) and mediate N-terminal modification of proteins (four examples) using a fluorescent-tethered diazo compound (15). A fluorescent group was conjugated to ubiquitin via 1-catalyzed alkene cyclopropanation with 15 in aqueous solution in two steps: (1) incorporation of an alkenic group by the reaction of N-hydroxysuccinimide ester 19 with ubiquitin and (2) cyclopropanation of the alkene-tethered Lys 6 ubiquitin (23) with the fluorescentlabeled diazoacetate 15 in the presence of a catalytic amount of 1. The corresponding cyclopropanation product (24) was obtained with -55% conversion based on MALDI-TOF mass spectrometry. The products 23, 24, and the N-terminal modified peptides and proteins were characterized by LC-MS/MS and/or SDS-PAGE analyses.
- Ho, Chi-Ming,Zhang, Jun-Long,Zhou, Cong-Ying,Chan, On-Yee,Yan, Jessie Jing,Zhang, Fu-Yi,Huang, Jie-Sheng,Che, Chi-Ming
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supporting information; scheme or table
p. 1886 - 1894
(2010/04/25)
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- Iron(III) corroles and porphyrins as superior catalysts for the reactions of diazoacetates with nitrogen- or sulfur-containing nucleophilic substrates: Synthetic uses and mechanistic insights
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A thorough mechanistic investigation has been performed on the reactions of primary and secondary amines with diazoacetates, which proceed uniquely quickly and efficiently when catalyzed by iron(III) corroles and porphyrins. Two major differences in relation to other metal-based catalysts are that the iron complexes are not poisoned by excess amine and that metal-carbene intermediates are apparently not involved in the reaction pathway. The results instead point towards nitrogen ylide intermediates formed by nucleophilic attack of the amines on diazoacetate-coordinated iron complexes. Nitrogen ylides are also formed when allyl- and propargylsubstituted tertiary amines react with diazoacetates, a scenario that smoothly leads to 2,3-rearrangement reaction products with catalytic amounts of the iron(III) complexes. Similar findings regarding the superiority of the iron-(III) complexes (in terms of catalyst loading, chemical yields, and reaction conditions) were obtained with thiols (S-H insertion) and sulfides (2,3-rear-rangement reactions), which suggest similar mechanisms operate in these cases.
- Aviv, Iris,Gross, Zeev
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scheme or table
p. 3995 - 4005
(2009/05/26)
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- A new method for generation of non-stabilized α-amino-substituted carbanions by the reaction of magnesium carbenoids with N-lithio arylamines: their reactivity and a new synthesis of α-amino acid derivatives
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Magnesium carbenoids were generated from aryl 1-chloroalkyl sulfoxides with i-PrMgCl in THF at low temperature in quantitative yields. The magnesium carbenoids were found to be reactive with N-lithio alkylamines to afford an olefin, which was derived from dimerization of the magnesium carbenoid, in moderate yield. On the other hand, reaction of the magnesium carbenoids with N-substituted N-lithio arylamines gave non-stabilized α-amino-substituted carbanions in good yields. Reactivity of the α-amino-substituted carbanions with some electrophiles was investigated and it was found that ethyl chloroformate reacted to give α-amino acid derivatives in good yields. As a whole, a new method for one-pot, three-component combined synthesis of α-amino acid derivatives from aryl 1-chloroalkyl sulfoxides was realized.
- Satoh, Tsuyoshi,Osawa, Atsushi,Ohbayashi, Tohru,Kondo, Atsushi
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p. 7892 - 7901
(2007/10/03)
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- ANILINO LIVER X-RECEPTOR MODULATORS
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The present invention is directed to selective LXR modulators, small molecule compounds corresponding to Formula I and is further directed to a process of treating a condition in a mammal that is modulated by LXR using a therapeutically effective dose of a compound of Formula I.
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- Dynamics of anilinium radical α-heterolytic fragmentation processes. Electrofugal group, substituent, and medium effects on desilylation, decarboxylation, and retro-aldol cleavage pathways
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A single electron transfer (SET) photosensitization technique in conjunction with time-resolved, laser spectroscopy has been employed to generate and kinetically analyze decay processes of anilinium radicals derived by one-electron oxidation of α-anilinocarboxylates, β- anilinoalcohols, and α-anilinosilanes. In this manner, the rates of unimolecular decarboxylation of aniliniumcarboxylate radicals were determined to be in the range 106 - 107 s-1 and dependent upon solvent polarity, the nature of the metal cation, and substituents on the aniline ring, nitrogen, and α-carbon. In addition, kinetic analysis of base-induced retro-aldol fragmentations of cation radicals arising by SET oxidation of β- anilinoalcohols has shown that they occur with bimolecular rate constants which vary from 104 to 105 M-1 s1. These values are close to those for α-deprotonation reactions of related N,N-dialkylanilinium radicals. The retro-aldol fragmentation rates, like those for α-decarboxylation, also vary in a patterned way with changes in arene ring, nitrogen, and α- and β- carbon substituents. An investigation of the dynamics of methanol-promoted reactions of α-(trimethylsilyl)methyl-substituted anilinium radicals, has demonstrated that a change in the nitrogen substituent from alkyl to acyl causes an ca. 10-fold increase in the desilylation rate. Parallel photochemical studies have been conducted to gain chemical evidence to support assignment of the anilinium radical decay pathways in the LFP experiments and to demonstrate the preparative consequences of the kinetic results. First, clean formation of products derived by coupling of the (N- methylanilino)methyl radical in photochemical reactions of 1,4- dicyanobenzene with either tetra-n-butylammonium N-methyl-N-phenylglycinate or β-(N-methyl-N-phenyl)aminoethanol shows that the respective decarboxylation and retro-aldol cleavage processes occur with exceptionally high efficiencies. Second, in accord with the high rates observed for aminium radical decarboxylation and base-induced retro-aldol fragmentation, tethered cyclohexenone - α-aminocarboxylates and - β-aminoethanols undergo high- yielding SET-promoted photocyclization reactions under both direct and SET- sensitized conditions. Last, results which depict how the rates of aminium radical α-fragmentation correlate with quantum efficiencies of SET-promoted reactions of tertiary amines and amides have come from a study of photocyclization reactions of N-(aminoethyl)- and (amidoethyl)phthalimides. The quantum yields for these SET-promoted processes are observed to vary with the electrofugal group and nitrogen substituent in the manner predicted on the basis of the LFP-determined fragmentation rates.
- Su, Zhuoyi,Mariano, Patrick S.,Falvey, Daniel E.,Yoon, Ung Chan,Oh, Sun Wha
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p. 10676 - 10686
(2007/10/03)
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- Insertion of ethyl diazoacetate into N-H and S-H bonds catalyzed by ruthenium porphyrin complexes
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Ruthenium porphyrin complexes catalyze insertion of ethyl diazoacetate into sulfur-hydrogen and nitrogen-hydrogen bonds under mild conditions and with reasonable to very good yields.
- Galardon, Erwan,Le Maux, Paul,Simonneaux, Gerard
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p. 2455 - 2456
(2007/10/03)
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- Conformation-Dependent Intramolecular Electron Transfer in N-(Aminoalkyl)-9-phenanthrenecarboxamides
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The molecular structure and photophysical behavior of several secondary and tertiary N-(aminoalkyl)phenanthrenecarboxamides have been investigated.Secondary (aminoalkyl)amides exist predominantly in the Z conformation, whereas tertiary amides exist as mixtures of Z and E conformers and semirigid piperazines as mixtures of chair conformers.Rate constants for endergonic intramolecular electron transfer are found to be highly dependent upon molecular structure.The aromatic and amide groups of the tertiary amides are essentially orthogonal, and thus, an E aminoalkyl group can adopt low-energy conformations in which there is spatial overlap between the aromatic and amine groups, whereas such overlap is not possible for either a Z aminoalkyl group or the piperazines.The observation of more rapid intramolecular electron transfer quenching of the phenanthrene singlet by an appended trialkylamine in the E vs Z conformation is attributed to this difference in overlap.An increase in the phenanthrene-amide dihedral angle is also found to result in a decrease in the rate constant for intramolecular electron transfer quenching by a Z aminoalkyl group.In the case of appended tertiary anilines, efficient electron transfer quenching occurs for both Z and E conformers.The Z conformers form fluorescent exciplexes, providing a new example of exciplex-type emission in the absence of direct ?-? overlap.Exciplexes formed by the E conformers are nonfluorescent and apparently undergo rapid intersystem crossing.The strong exciplex emission observed at low temperatures both in solution and in frozen glasses is attributed to ground state dimers or aggregates.
- Lewis, Frederick D.,Burch, Erick L.
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p. 4055 - 4063
(2007/10/03)
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- SYNTHESIS OF BAPTA-AM ANALOGUES CAPABLE OF ENHANCING THE VASCULAR PRODUCTION OF PROSTACYCLIN
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About 30 analogues of BAPTA-AM, a potential antithrombotic agent, have been synthesized and tested for their effect on the production of prostacyclin.None of them was found to be a better enhancher of the production of prostacyclin by aortic endothelial cells than BAPTA-AM itself.The enhancing effect can be produced by compounds unable to chelate Ca2+, thus confirming that it is not related to their buffering capacity for free Ca2+.
- Heilporn, S.,Broeders, F.,Daloze, D.,Braekman, J. C.,Boeynaems, J. M.
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p. 309 - 320
(2007/10/02)
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- Synthesis, spectral studies and biological activities of some N-bridged heterocycles derived from 3-arylaminomethyl-4-amino-5-mercapto-1,2,4- triazoles
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Synthesis of four 3-arylaminomethyl-4-amino-5-mercapto-1,2,4-triazoles starting from substituted anilines is described. These triazoles were employed in the synthesis of some N-bridged heterocycles carrying arylaminomethyl substituents. All the newly synthesized compounds were characterized by analytical, NMR and mass spectral studies. Some of the newly synthesized compounds were screened for their antibacterial and antiviral properties.
- Holla,Udupa
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p. 305 - 318
(2007/10/02)
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