- Synthesis, crystal structures, and optical properties of the π-π interacting pyrrolo[2,3-b]quinoxaline derivatives containing 2-thienyl substituent
-
Three (E/Z)-diastereoisomers, based on pyrrolo[2,3-b]quinoxaline system as fluorophore and containing: 2-thienylmethyl (1), bis(2-thienylmethyl)-2-aminoethyl (3a), bis(2-thienylmethyl)-3-aminopropyl (3b) groups as substituents, were synthesized and characterized by X-ray structural analysis, PXRD, NMR, UV–Vis as well as fluorescence. These compounds are non-fluorescent in acetonitrile solution, however, they exhibit aggregation induced emission enhancement (AIEE) upon water addition and in solid state. X-ray structural analysis revealed that molecules with 2-thienylmethyl and bis(2-thienylmethyl)-2-aminoethyl groups form dimers and π-stacks through π-π interactions between anitiparallel oriented pyrroloquinoxaline cores with interplanar distances 3.45 ? and 3.20 ?, respectively. Conformation of bis(2-thienylmethyl)-3-aminopropyl group is imposed by incorporated DMSO-d6 solvent molecule and weak intermolecular S-π and CH-π interactions, that prevents π-π interaction between fluorophore cores. The correlation between crystal structure and fluorescent properties of synthesized molecules was discussed. The DFT calculations were performed to rationalize the differences between considered systems.
- Goszczycki, Piotr,Stadnicka, Katarzyna,Brela, Mateusz Z.,Grolik, Jaros?aw,Ostrowska, Katarzyna
-
-
Read Online
- Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
-
Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
- Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
-
p. 2059 - 2067
(2021/09/02)
-
- Indirect reduction of CO2and recycling of polymers by manganese-catalyzed transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes
-
The reduction of polar bonds, in particular carbonyl groups, is of fundamental importance in organic chemistry and biology. Herein, we report a manganese pincer complex as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and even polyurethanes leading to the corresponding alcohols, amines, and methanol as products. Since these compound classes can be prepared using CO2as a C1 building block the reported reaction represents an approach to the indirect reduction of CO2. Notably, these are the first examples on the reduction of carbamates and urea derivatives as well as on the C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is highlighted by the successful reduction of 12 urea derivatives, 26 carbamates and 11 amides. The corresponding amines, alcohols and methanol were obtained in good to excellent yields up to 97%. Furthermore, polyurethanes were successfully converted which represents a viable strategy towards a circular economy. Based on control experiments and the observed intermediates a feasible mechanism is proposed.
- Liu, Xin,Werner, Thomas
-
p. 10590 - 10597
(2021/08/20)
-
- Comparative account of catalytic activity of Ru- and Ni-based nanocomposites towards reductive amination of biomass derived molecules
-
This work includes an effective comparison of metallic ruthenium and nickel nanoparticles loaded on montmorillonite clay (MMT) for reductive amination reaction of biomass-derived molecules. It comprises an eco-friendly reaction using water as a solvent, utilizing molecular hydrogen and liquor ammonia (25% aq. solution) for the synthesis of primary amines from bio-derived aldehydes within 3–10 h of reaction time. Various parameters such as temperature, hydrogen pressure, substrate/ammonia concentration ratio, and reaction time were optimized while comparing the selectivity of primary amines for both catalysts. The applicability scope of these catalysts was explored with a library of aryl and heterocyclic aldehydes. The reductive amination of crude furfural extracted from biomass feedstock (rice husk) and pure xylose sugar was tested, showing yields in the range of 11–36%, to show the wider industrial scope of both nanocomposites. Gram scale conversion was also carried out to showcase the bulk scalability of the Ru/MMT catalyst.
- Bhanage, Bhalchandra M.,Gokhale, Tejas A.,Raut, Amol B.
-
-
- Benzimidazole fragment containing Mn-complex catalyzed hydrosilylation of ketones and nitriles
-
The synthesis of a new bidentate (NN)–Mn(I) complex is reported and its catalytic activity towards the reduction of ketones and nitriles is studied. On comparing the reactivity of various other Mn(I) complexes supported by benzimidazole ligand, it was observed that the Mn(I) complexes bearing 6-methylpyridine and benzimidazole fragments exhibited the highest catalytic activity towards monohydrosilylation of ketones and dihydrosilylation of nitriles. Using this protocol, a wide range of ketones were selectively reduced to the corresponding silyl ethers. In case of unsaturated ketones, the chemoselective reduction of carbonyl group over olefinic bonds was observed. Additionally, selective dihydrosilylation of several nitriles were also achieved using this complex. Mechanistic investigations with radical scavengers suggested the involvement of radical species during the catalytic reaction. Stoichiometric reaction of the Mn(I) complex with phenylsilane revealed the formation of a new Mn(I) complex.
- Ganguli, Kasturi,Mandal, Adarsha,Sarkar, Bidisha,Kundu, Sabuj
-
supporting information
(2020/08/13)
-
- Synthesis of oxalamides by acceptorless dehydrogenative coupling of ethylene glycol and amines and the reverse hydrogenation catalyzed by ruthenium
-
A sustainable, new synthesis of oxalamides, by acceptorless dehydrogenative coupling of ethylene glycol with amines, generating H2, homogeneously catalyzed by a ruthenium pincer complex, is presented. The reverse hydrogenation reaction is also accomplished using the same catalyst. A plausible reaction mechanism is proposed based on stoichiometric reactions, NMR studies, X-ray crystallography as well as observation of plausible intermediates.
- Ben-David, Yehoshoa,Diskin-Posner, Yael,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
-
p. 7188 - 7193
(2020/07/23)
-
- General and selective synthesis of primary amines using Ni-based homogeneous catalysts
-
The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H2metathesis as the rate-determining step.
- Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Jiao, Haijun,Murugesan, Kathiravan,Wei, Zhihong
-
p. 4332 - 4339
(2020/05/18)
-
- Design, synthesis and the structure-activity relationship of agonists targeting on the ALDH2 catalytic tunnel
-
ALDH2, a key enzyme in the alcohol metabolism process, detoxifies several kinds of toxic small molecular aldehydes, which induce severe organ damages. The development of novel Alda-1 type ALDH2 activators was mostly relied on HTS but not rational design so far. To clarify the structure–activity relationship (SAR) of the skeleton of Alda-1 analogs by synthesis of the least number of analogs, we prepared 31 Alda-1 analogs and 3 isoflavone derivatives and evaluated for their ALDH2-activating activity. Among these, the ALDH2-activating activity of mono-halogen-substituted (Cl and Br) N-piperonylbenzamides 3b and 3 k, and non-aromatic amides 8a-8c, were 1.5–2.1 folds higher than that of Alda-1 at 20 μM. The relationship between binding affinity in computer aided molecular docking model and the ALDH2-activating activity assays were clarified as follows: for Alda-1 analogs, with the formation of halogen bonds, the enzyme-activating activity was found to follow a specific regression curve within the range between ?5 kcal/mol and ?4 kcal/mol. For isoflavone derivatives, the basic moiety on the B ring enhance the activating activity. These results provide a new direction of utilizing computer-aided modeling to design novel ALDH2 agonists in the future.
- Cheng, Ming-Che,Lo, Wei-Chi,Chang, Yu-Wen,Lee, Shoei-Sheng,Chang, Chia-Chuan
-
-
- Facile synthesis of controllable graphene-co-shelled reusable Ni/NiO nanoparticles and their application in the synthesis of amines under mild conditions
-
The primary objective of many researchers in chemical synthesis is the development of recyclable and easily accessible catalysts. These catalysts should preferably be made from Earth-abundant metals and have the ability to be utilised in the synthesis of pharmaceutically important compounds. Amines are classified as privileged compounds, and are used extensively in the fine and bulk chemical industries, as well as in pharmaceutical and materials research. In many laboratories and in industry, transition metal catalysed reductive amination of carbonyl compounds is performed using predominantly ammonia and H2. However, these reactions usually require precious metal-based catalysts or RANEY nickel, and require harsh reaction conditions and yield low selectivity for the desired products. Herein, we describe a simple and environmentally friendly method for the preparation of thin graphene spheres that encapsulate uniform Ni/NiO nanoalloy catalysts (Ni/NiO?C) using nickel citrate as the precursor. The resulting catalysts are stable and reusable and were successfully used for the synthesis of primary, secondary, tertiary, and N-methylamines (more than 62 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, and H2 under very mild industrially viable and scalable conditions (80 °C and 1 MPa H2 pressure, 4 h), offering cost-effective access to numerous functionalized, structurally diverse linear and branched benzylic, heterocyclic, and aliphatic amines including drugs and steroid derivatives. We have also demonstrated the scale-up of the heterogeneous amination protocol to gram-scale synthesis. Furthermore, the catalyst can be immobilized on a magnetic stirring bar and be conveniently recycled up to five times without any significant loss of catalytic activity and selectivity for the product.
- Cui, Zhibing,Liu, Jianguo,Liu, Qiying,Ma, Longlong,Singh, Thishana,Wang, Chenguang,Wang, Nan,Zhu, Yuting
-
supporting information
p. 7387 - 7397
(2020/11/19)
-
- Design and synthesis of heteroaromatic-based benzenesulfonamide derivatives as potent inhibitors of H5N1 influenza A virus
-
Influenza A virus is an enveloped negative single-stranded RNA virus that causes febrile respiratory infection and represents a clinically challenging threat to human health and even lives worldwide. Even more alarming is the emergence of highly pathogenic avian influenza (HPAI) strains such as H5N1, which possess much higher mortality rate (60%) than seasonal influenza strains in human infection. In this study, a novel series of heteroaromatic-based benzenesulfonamide derivatives were identified as M2 proton channel inhibitors. A systematic investigation of the structure-activity relationships and a molecular docking study demonstrated that the sulfonamide moiety and 2,5-dimethyl-substituted thiophene as the core structure played significant roles in the anti-influenza activity. Among the derivatives, compound 11k exhibited excellent antiviral activity against H5N1 virus with an EC50 value of 0.47 μM and selectivity index of 119.9, which are comparable to those of the reference drug amantadine.
- Yu, Yongshi,Tazeem,Xu, Zhichao,Du, Liaoqi,Jin, Mengyu,Dong, Chune,Zhou, Hai-Bing,Wu, Shuwen
-
-
- Old Concepts, New Application – Additive-Free Hydrogenation of Nitriles Catalyzed by an Air Stable Alkyl Mn(I) Complex
-
An efficient additive-free manganese-catalyzed hydrogenation of nitriles to primary amines with molecular hydrogen is described. The pre-catalyst, a well-defined bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dpre)(CO)3(CH3)] (dpre=1,2-bis(di-n-propylphosphino)ethane), undergoes CO migratory insertion into the manganese-alkyl bond to form acyl complexes which upon hydrogenolysis yields the active coordinatively unsaturated Mn(I) hydride catalyst [Mn(dpre)(CO)2(H)]. A range of aromatic and aliphatic nitriles were efficiently and selectively converted into primary amines in good to excellent yields. The hydrogenation of nitriles proceeds at 100 °C with a catalyst loading of 2 mol % and a hydrogen pressure of 50 bar. Mechanistic insights are provided by means of DFT calculations. (Figure presented.).
- Weber, Stefan,Veiros, Luis F.,Kirchner, Karl
-
p. 5412 - 5420
(2019/11/13)
-
- Synthesis and biological evaluation of some novel thiophene-bearing quinazoline derivatives as EGFR inhibitors
-
Background: With the approval of gefitinib, erlotinib, afatinib, and osimertinib for clinical use, targeting Epidermal Growth Factor Receptor (EGFR) has been intensively pursued. Similar to most therapies, challenges related to the treatment resistance against these drugs have emerged over time, so new EGFR Tyrosine Kinase Inhibitors (TKIs) need to be developed. This study aimed to investigate the potential use of a series of thiophene-bearing quinazoline derivatives as EGFR inhibitors. We designed and synthesized nine quinazolin derivatives, among which five compounds (5e, 5f, 5g, 5h, and 5i) were reported for the first time. Methods: Two cancer cell lines, A431 (overexpressing EGFR) and A549 (EGFR wild-type and K-ras mutation), were treated by these compounds and subjected to MTT assay. The A431 cells were selected for further treatment (5e) and Western blot analysis. Results: Although the compounds exerted no obvious effects on the proliferation of A549 cells, seven out of the nine compounds significantly inhibited the growth of A431 cells. In particular, the IC50 values of 5e and erlotinib were nearly equal. Western blot results showed that 5e significantly inhibited EGFR autophosphorylation in A431 cells. Structure-activity relationships indicated that quinazolines bearing 6,7-side chains were more potent than those unsubstituted at the 6,7-positions. Moreover, electron-withdrawing hydrophobic groups on the 5-position of the thiophene were preferred, such as chlorine or bromine atom. Conclusion: Nine 4-aminoquinazolin derivatives were designed, synthesized, and evaluated against A431 and A549 cell lines. Seven compounds significantly inhibited the growth of A431 cells. In particular, 5e possessed similar antitumor potency to that of erlotinib.
- Zou, Min,Jin, Bo,Liu, Yanrong,Chen, Huiping,Zhang, Zhuangli,Zhang, Changzheng,Zhao, Zhihong,Zheng, Liyun
-
p. 102 - 110
(2019/01/04)
-
- Selective synthesis of mono- and di-methylated amines using methanol and sodium azide as C1 and N1 sources
-
A Ru(ii) complex mediated synthesis of various N,N-dimethyl and N-monomethyl amines from organic azides using methanol as a methylating agent is reported. This methodology was successfully applied for a one-pot reaction of bromide derivatives and sodium azide in methanol. Notably, by controlling the reaction time several N-monomethylated and N,N-dimethylated amines were synthesized selectively. The practical applicability of this tandem process was revealed by preparative scale reactions with different organic azides and synthesis of an anti-vertigo drug betahistine. Several kinetic experiments and DFT studies were carried out to understand the mechanism of this transformation.
- Chakrabarti, Kaushik,Mishra, Anju,Panja, Dibyajyoti,Paul, Bhaskar,Kundu, Sabuj
-
supporting information
p. 3339 - 3345
(2018/07/29)
-
- Hydrogenation of Nitriles and Ketones Catalyzed by an Air-Stable Bisphosphine Mn(I) Complex
-
Efficient hydrogenations of nitriles and ketones with molecular hydrogen catalyzed by a well-defined bench-stable bisphosphine Mn(I) complex are described. These reactions are environmentally benign and atomically economic, implementing an inexpensive, earth-abundant nonprecious metal catalyst. A range of aromatic and aliphatic nitriles and ketones were efficiently converted into primary amines and alcohols, respectively, in good to excellent yields. The hydrogenation of nitriles proceeds at 100 °C with catalyst loading of 2 mol % and 20 mol % base (t-BuOK), while the hydrogenation of ketones takes place already at 50 °C, with a catalyst loading of 1 mol % and 5 mol % of base. In both cases, a hydrogen pressure of 50 bar was applied.
- Weber, Stefan,St?ger, Berthold,Kirchner, Karl
-
supporting information
p. 7212 - 7215
(2018/11/25)
-
- Synthesis method of 2-thienylmethylamine
-
The invention relates to a synthesis method of 2-thienylmethylamine. According to the method, raw materials of 2-acetylthiophene, ethyl alcohol, concentrated ammonia water and sulphur powder take a reaction under the condition of 0.08 to 2.00 MPa to produce the 2-thienylacetamide; the 2-thienylacetamide and sodium hypochlorite or sodium hypobromite are prepared into 2-thienylmethylamine through Hofmann degradation under the effect of liquid caustic soda. The synthesis method has the advantages that the raw materials can be easily obtained; the process is simple and controllable; the maneuverability is high; the purity of the prepared finished product is high; the yield is high.
- -
-
Paragraph 0004; 0012; 0015; 0018; 0022
(2017/08/28)
-
- Synthesis method of 2-thienylmethylamine
-
The invention belongs to the field of organic synthesis and in particular relates to a synthesis method of 2-thienylmethylamine. The synthesis method comprises the following steps: adding 2-thiophenecarboxaldehyde, a solvent, hydroxylamine inorganic acid salt and water into a reactor; stirring and dissolving to sufficiently mix the raw materials; adding acid into the reactor; meanwhile, adding zinc powder in batches; controlling temperature and time to enable the raw materials in a mixed solution in the reactor to sufficiently react; after reacting, dripping ammonia water and a sodium hydroxide water solution respectively; sufficiently stirring and displacing the 2-thiophenecarboxaldehyde; filtering, extracting, decompressing and rectifying to obtain a finished-product of the 2-thiophenecarboxaldehyde. The synthesis method has the advantages that the raw materials are cheap and easy to obtain, the dosage of the zinc powder is less, and the process is simple; the rectified target product 2-thiophenecarboxaldehyde has relatively good quality, and the mol yield (of the 2-thiophenecarboxaldehyde) reaches 61 percent or more.
- -
-
Paragraph 0037; 0038; 0039; 0040; 0041
(2017/08/29)
-
- NHC-based coordination polymers as solid molecular catalysts for reductive amination of biomass levulinic acid
-
A class of robust solid molecular NHC-based catalysts were readily fabricated via self-assembly from a p-phenylene-bridged bis-benzimidazolium salt with selected metal precursors. Among them, the NHC-Ru polymer demonstrated high catalytic activity and excellent stability as a solid molecular catalyst for the solvent-free reductive amination of biomass levulinic acid with inexpensive ammonium formate, furnishing a challenging unprotected 5-methyl-2-pyrrolidone quantitatively at a 0.15 mol% catalyst loading. The solid catalyst was readily recovered and reused for 37 runs without obvious loss of activity. Remarkably, a TON value up to 6.7 × 104 was achieved in a molar-scale reaction with a catalyst loading at 0.001 mol%. Inspired by the results of a preliminary mechanistic study, notably, one-pot tandem reductive reactions of LA with aldehydes or ketones were successfully developed, affording a variety of structurally intriguing and functional N-substituted 5-methyl-2-pyrrolidones in high chemo-selectivity with good to excellent yields.
- Sun, Zheming,Chen, Jiangbo,Tu, Tao
-
p. 789 - 794
(2017/08/18)
-
- Electronic Effect of Ruthenium Nanoparticles on Efficient Reductive Amination of Carbonyl Compounds
-
Highly selective synthesis of primary amines over heterogeneous catalysts is still a challenge for the chemical industry. Ruthenium nanoparticles supported on Nb2O5 act as a highly selective and reusable heterogeneous catalyst for the low-temperature reductive amination of various carbonyl compounds that contain reduction-sensitive functional groups such as heterocycles and halogens with NH3 and H2 and prevent the formation of secondary amines and undesired hydrogenated byproducts. The selective catalysis of these materials is likely attributable to the weak electron-donating capability of Ru particles on the Nb2O5 surface. The combination of this catalyst and homogeneous Ru systems was used to synthesize 2,5-bis(aminomethyl)furan, a monomer for aramid production, from 5-(hydroxymethyl)furfural without a complex mixture of imine byproducts.
- Komanoya, Tasuku,Kinemura, Takashi,Kita, Yusuke,Kamata, Keigo,Hara, Michikazu
-
supporting information
p. 11493 - 11499
(2017/08/30)
-
- MOF-derived cobalt nanoparticles catalyze a general synthesis of amines
-
The development of base metal catalysts for the synthesis of pharmaceutically relevant compounds remains an important goal of chemical research. Here, we report that cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts. Their convenient and practical preparation entailed template assembly of cobaltdiamine- dicarboxylic acid metal organic frameworks on carbon and subsequent pyrolysis under inert atmosphere.The resulting stable and reusable catalysts were active for synthesis of primary, secondary, tertiary, and N-methylamines (more than 140 examples).The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, or nitro compounds, and molecular hydrogen under industrially viable and scalable conditions, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets.
- Jagadeesh, Rajenahally V.,Murugesan, Kathiravan,Alshammari, Ahmad S.,Neumann, Helfried,Pohl, Marga-Martina,Radnik, J?rg,Beller, Matthias
-
p. 326 - 332
(2017/09/28)
-
- Synthesis and Biological Evaluation of Novel 2-Aminonicotinamide Derivatives as Antifungal Agents
-
Based on the structures of the reported compounds G884 [N-(3-(pentan-2-yloxy)phenyl)nicotinamide], E1210 [3-(3-(4-((pyridin-2-yloxy)methyl)benzyl)isoxazol-5-yl)pyridin-2-amine], and 10 b [2-amino-N-((5-(3-fluorophenoxy)thiophen-2-yl)methyl)nicotinamide], which inhibit the biosynthesis of glycosylphosphatidylinositol (GPI)-anchored proteins in fungi, a series of novel 2-aminonicotinamide derivatives were designed, synthesized, and evaluated for in vitro antifungal activity. Most of these compounds were found to exhibit potent in vitro antifungal activity against Candida albicans, with MIC80values ranging from 0.0313 to 4.0 μg mL?1. In particular, compounds 11 g [2-amino-N-((5-(((2-fluorophenyl)amino)methyl)thiophen-2-yl)methyl)nicotinamide] and 11 h [2-amino-N-((5-(((3-fluorophenyl)amino)methyl)thiophen-2-yl)methyl)nicotinamide] displayed excellent activity against C. albicans, with MIC80values of 0.0313 μg mL?1, and exhibited broad-spectrum antifungal activity against fluconazole-resistant C. albicans, C. parapsilosis, C. glabrata, and Cryptococcus neoformans, with a MIC80range of 0.0313–2.0 μg mL?1. Further studies by electron microscopy and laser confocal microscopy indicated that compound 11 g targets the cell wall and decreases GPI anchor content on the cell surface of C. albicans.
- Ni, Tingjunhong,Li, Ran,Xie, Fei,Zhao, Jing,Huang, Xin,An, Maomao,Zang, Chengxu,Cai, Zhan,Zhang, Dazhi,Jiang, Yuanying
-
p. 319 - 326
(2017/03/01)
-
- Efficient chemoselective hydrogenation of organic azides catalyzed by palladium nanoparticles with alkyne-derived homogeneous supports
-
Catalytic chemoselective hydrogenation of organic azides using palladium nanoparticles stabilized by alkyne derivatives was studied. A broad range of aromatic and aliphatic azides were smoothly reduced to the corresponding amines in excellent yields with a quite small amount of the catalyst. Hydrogenation of 3-phenylpropylazide gave 3-phenylpropylamine almost quantitatively with a substrate-to-palladium molar ratio (S/Pd) of 12,900 under 8?atm of H2. The reaction under 1?atm of H2also proceeded smoothly with an S/Pd of 1000. Several reduction-sensitive functional groups, such as carbonyl, halide, benzylic OH, and aliphatic nitro were well tolerated under the reaction conditions.
- Arai, Noriyoshi,Onodera, Nozomi,Ohkuma, Takeshi
-
supporting information
p. 4183 - 4186
(2016/08/24)
-
- NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions
-
A series of seven novel NImNHP-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(NImNHPtBu)] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions.
- Adam, Rosa,Alberico, Elisabetta,Baumann, Wolfgang,Drexler, Hans-Joachim,Jackstell, Ralf,Junge, Henrik,Beller, Matthias
-
p. 4991 - 5002
(2016/04/05)
-
- Selective catalytic hydrogenation of nitriles to primary amines using iron pincer complexes
-
The selective catalytic hydrogenation of nitriles to primary amines with the well-defined Fe(PNPCy) pincer complex 2 is reported. This iron pincer catalyst shows superior catalytic activity and selectivity in the reduction of various nitriles including industrially relevant adipodinitrile in high yields under relatively mild conditions.
- Lange,Elangovan,Cordes,Spannenberg,Jiao,Junge,Bachmann,Scalone,Topf,Junge,Beller
-
p. 4768 - 4772
(2016/07/11)
-
- A Mild and Base-Free Protocol for the Ruthenium-Catalyzed Hydrogenation of Aliphatic and Aromatic Nitriles with Tridentate Phosphine Ligands
-
A novel protocol for the general hydrogenation of nitriles in the absence of basic additives is described. The system is based on the combination of [Ru(cod)(methylallyl)2] (cod=cyclooctadiene) and L2. A variety of aromatic and aliphatic nitriles is hydrogenated under mild conditions (50 °C and 15 bar H2) with this system. Kinetic studies revealed higher activity in the case of aromatic nitriles compared with aliphatic ones.
- Adam, Rosa,Bheeter, Charles Beromeo,Jackstell, Ralf,Beller, Matthias
-
p. 1329 - 1334
(2016/04/20)
-
- HIV INTEGRASE INHIBITORS
-
The present invention features compounds that are HIV integrase inhibitors and therefore are useful in the inhibition of HIV replication, the prevention and/or treatment of infection by HIV, and in the treatment of AIDS and/or ARC.
- -
-
-
- APPLICATIONS OF N6-SUBSTITUTED ADENOSINE DERIVATIVE AND N6-SUBSTITUTED ADENINE DERIVATIVE TO CALMING, HYPNOSES, CONVULSION RESISTANCE, EPILEPTIC RESISTANCE, PARKINSON DISEASE RESISTANCE, AND DEMENTIA PREVENTION AND TREATMENT
-
PROBLEM TO BE SOLVED: To prepare analgesics, hypnotic agents, anticonvulsant agents, antiepileptics, antiparkinson drugs, dementia prophylactics, and health care food. SOLUTION: The present invention relates to an N6-substituted adenosine derivative and an N6-substituted adenine derivative selected from the group consisting of specific compounds. The present invention also relates to a pharmaceutical composition at least comprising a therapeutically effective amount of the compounds and a pharmaceutically acceptable carrier. The invention further relates to the compounds used in preparation of analgesics, hypnotic agents, anticonvulsant agents, antiepileptics, antiparkinson drugs, dementia prophylactics, and health care food. COPYRIGHT: (C)2016,JPO&INPIT
- -
-
Paragraph 0111
(2018/10/27)
-
- Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst
-
Selective catalytic reductions of nitriles are presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including industrially important adipodinitrile are hydrogenated to the corresponding primary amines. Modelling suggests the reaction follows an outer sphere hydrogenation mechanism. An efficient and selective catalytic reduction of nitriles is presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including the industrially important adipodinitrile are hydrogenated to the corresponding primary amines. The reaction follows an outer-sphere mechanism.
- Neumann, Jacob,Bornschein, Christoph,Jiao, Haijun,Junge, Kathrin,Beller, Matthias
-
supporting information
p. 5944 - 5948
(2015/09/22)
-
- Homogeneous hydrogenation of nitriles catalyzed by molybdenum and tungsten amides
-
Low-valent molybdenum and tungsten amides M(NO)(CO)(PNP) {M = Mo, 1a; W, 1b; PNP = N(CH2CH2PiPr2) 2} were found to be active catalysts for the hydrogenation of various nitriles to the corresponding imines, primary amines, and N-substituted imines with high selectivity for the latter type of product. A wide range of p-and m-substituted aromatic nitriles-p-methyl, p-methoxy, p-bromobenzonitriles; 3-trifluoromethylbenzonitrile, m-and p-disubstituted benzonitrile; the heterocyclic 2-thiophencarbonitrile; and the aliphatic nitriles cyclohexylcarbonitrile and benzylcyanide-could be hydrogenated at 140 °C and 60 bar H2 in THF with high yields. TOFs were found to be between 0.4 and 36 h-1.
- Chakraborty, Subrata,Berke, Heinz
-
p. 2191 - 2194
(2014/07/21)
-
- CuI-catalyzed coupling of gem-dibromovinylanilides and sulfonamides: An efficient method for the synthesis of 2-amidoindoles and indolo[1,2-a] quinazolines
-
A Cu(I)-catalyzed, intermolecular protocol for the synthesis of 2-amidoindoles and tetrahydroindolo[1,2-a]quinazolines in shorter time and high yields is reported. The key highlight of this disclosure is the formation of 2-amidoindole and tetrahydroindolo[1,2-a]quinazoline moieties directly from gem-dibromovinylanilides and sulfonamides in a one-pot fashion through the in situ formation of ynamides followed by a base-promoted intramolecular hydroamidation.
- Kiruthika, Selvarangam E.,Perumal, Paramasivan Thirumalai
-
supporting information
p. 484 - 487
(2014/04/03)
-
- Synthesis of pyrrolo-/indolo[1,2-a ]quinolines and naphtho[2,1- b ]thiophenes from gem -dibromovinyls and sulphonamides
-
A highly efficient and simple route for the synthesis of pyrrolo-/indolo[1,2-a]quinolines and naphtho[2,1-b]thiophenes from gem-dibromovinyls and sulphonamides is reported. The noteworthy feature of this report is that the methodology involves a two-step protocol to synthesize tri- and tetracyclic heterocycles in a one-pot fashion through the Cu(I)-catalyzed formation of ynamide followed by a Ag(I)-assisted intramolecular hydroarylation. The photophysical properties of representative examples of pyrrolo- and indolo[1,2-a]quinolines in solid and solution states have also been studied.
- Kiruthika, Selvarangam E.,Nandakumar, Avanashiappan,Perumal, Paramasivan Thirumalai
-
supporting information
p. 4424 - 4427
(2015/02/05)
-
- Selective reduction of amides to amines by boronic acid catalyzed hydrosilylation
-
Not a 'B'ore! Benzothiophene-based boronic acids catalyze the reduction of tertiary, secondary, and primary amides in the presence of a hydrosilane. The reaction demonstrates good functional-group tolerance. Copyright
- Li, Yuehui,Molina De La Torre, Jesus A.,Grabow, Kathleen,Bentrup, Ursula,Junge, Kathrin,Zhou, Shaolin,Brueckner, Angelika,Beller, Matthias
-
p. 11577 - 11580
(2013/11/06)
-
- N6-SUBSTITUTED ADENOSINE DERIVATIVES AND N6-SUBSTITUTED ADENINE DERIVATIVES AND USES THEREOF
-
The present invention provides N6-substituted adenosine derivatives and N6-substituted adenine derivatives, manufacturing methods thereof, a pharmaceutical composition comprising the said compounds above, and uses of these compounds in manufacturing medicaments and health-care products for treating insomnia, convulsion, epilepsy, and Parkinson's diseases, and preventing and treating dementia.
- -
-
Paragraph 0146
(2013/03/26)
-
- N6-SUBSTITUTED ADENOSINE DERIVATIVES, N6-SUBSTITUTED ADENINE DERIVATIVES AND USES THEREOF
-
The present invention provides N6-substituted adenosine derivatives and N6-substituted adenine derivatives, manufacturing methods thereof, a pharmaceutical composition comprising the said compounds above, and uses of of these compounds in manufacturing medicaments and health-care products for treating insomnia, convulsion, epilepsy, and Parkinson's diseases, and preventing and treating dementia.
- -
-
Page/Page column 47
(2012/11/06)
-
- Application of flow chemistry to the reduction of nitriles to aldehydes
-
Reduction of nitriles to aldehydes with diisobutylaluminium hydride (DIBAL-H) is an important transformation in organic chemistry. But the use of this reaction is limited for the lack of reproducibility due to the instability of the intermediates formed. In the current article we disclose the improvement of the reaction applying continuous flow technology.
- Mu?oz, Juan De M.,Alcázar, Jesús,De La Antonio, Hoz,Díaz-Ortiz, Angel
-
experimental part
p. 6058 - 6060
(2011/11/29)
-
- Assembling p-type molecules on single wall carbon nanotubes for photovoltaic devices
-
We report the design and synthesis of an oligothiophene molecule that noncovalently functionalizes carbon nanotubes to create a hybrid material for photovoltaic devices.
- Klare, Jennifer E.,Murray, Ian P.,Goldberger, Joshua,Stupp, Samuel I.
-
supporting information; experimental part
p. 3705 - 3707
(2009/12/01)
-
- Voltammetric, potentiometric and spectrophotometric studies of some hydrazones and their metal complexes in ethanolic-aqueous buffered solutions
-
The electrochemical behavior of some hydrazones derived from 6-chloro-2-hydrazinopyridine in the Britton-Robinson universal buffer of pH 2-11 containing 35% ethanol was investigated at the mercury electrode using dc-polarography, controlled-potential coulometry, and cyclic voltammetry techniques. The examined hydrazones were reduced in solutions of pH 2 single bond. The mechanistic pathway of the electrode reaction of the studied compounds was elucidated and discussed. The pK a values of the examined hydrazones and the stoichiometry of their complexes in solution with some transition metal ions were determined spectrophotometrically. The dissociation constants and the thermodynamic parameters of the investigated hydrazones, and the stability constants of their metal complexes in solution were determined potentiometrically. Springer-Verlag 2006.
- Ghoneim, Mohammed M.,El-Hallag, Ibrahim S.,El-Baradie, Kamal Y.,El-Desoky, Hanaa S.,El-Attar, Mona A.
-
p. 285 - 299
(2007/10/03)
-
- SUBSTITUTED QUINAZOLINE DERIVATIVES AND THEIR USE AS INHIBITORS
-
The use of a compound of formula (I) 1 or a salt, ester or amide thereof; where X is O, or S, S(O) or S(O)2, or NR6 where R6 is hydrogen or C1-6 alkyl,; R5 is an optionally substituted 5-membered heteroaromatic ring, R1, R2 ,R3, R4 are independently selected from various specified moieties, in the preparation of a medicament for use in the inhibition of aurora 2 kinase. Certain compounds are novel and these, together with pharmaceutical compositions containing them are also described and claimed
- -
-
-
- Pharmaceutically active pyrrolidine derivatives
-
The present invention is related to pyrrolidine derivatives of formula (I). Said compounds are preferably for use as pharmaceutically active compounds. Specifically, pyrrolidine derivatives of formula (I) are useful in the treatment and/or prevention of premature labor, premature birth and dysmenorrhea. In particular, the present invention is related to pyrrolidine derivatives displaying a substantial modulatory, notably an antagonist activity of the oxytocin receptor. More preferably, said compounds are useful in the treatment and/or prevention of disease states mediated by oxytocin, including premature labor, premature birth and dysmenorrhea. The present invention is furthermore related to novel pyrrolidine derivatives as well as to methods of their preparation, wherein X is selected from the group consisting of CR6R7, NOR6, NNR6R7; A is selected from the group consisting of —(C═O)—, —(C═O)—O—, —C(═NH)—, —(C═O)—NH—, —(C═S)—NH, —SO22—, —SO2NH—, —CH2—,B is either a group —(C═O)—NR8R9 or represents a heterocyclic residue having the formula (a) wherein Q is NR10, O or S; n is an integer selected of 0, 1 or 2; Y, Z and E form together with the 2 carbons to which they are attached a 5-6 membered aryl or heteroaryl ring.
- -
-
-
- Pharmaceutically active pyrrolidine derivatives as bax inhibitors
-
The present invention is related to new substituted pyrrolidine derivatives of formula (I). Said compounds are preferably for use as pharmaceutically active compounds. Specifically, pyrrolidine derivatives of formula (I) are useful in the treatment and/or prevention of neurodegenerative disorders, diseases associated with polygultamine tracts, epilepsy, ischemia, infertility, cardiovascular disorders renal hypoxia, hepatitis and AIDS. Said pyrrolidine derivatives display a modulatory and most notably a down-regulating-up to an inhibitory-activity with respect to the cellular death agonist Bax and/or the activation pathways leading to Bax and allows therefore to block the release of cytochrome (c). The present invention is furthermore related to novel pharmaceutically activity substituted pyrrolidine derivatives as well as to methods of their preparation, wherein X is selected from the group consisting of O, S, CRR, NOR, NNRR; A is selected from the group consisting of —(C═O)—, —(C═O)—O—, —C(═NH)—, —(C═O)—NH—, —(C═S)—NH, —SO2-, —SO2NH—; —CH2-; B is either a group —(C═O)—NRR or represents a heterocyclic residue having the formula (II) wherein Q is NR, O or S; n is an integer selected of 0, 1 or 2; Y, Z and E form together with the 2 carbons to which they are attached a 5-6 membered aryl or heteroaryl ring.
- -
-
-
- Design, synthesis, and biological evaluation of new inhibitors of the endocannabinoid uptake: Comparison with effects on fatty acid amidohydrolase
-
A new series of arachidonic acid derivatives were synthesized and evaluated as inhibitors of the endocannabinoid uptake. Most of them are able to inhibit anandamide uptake with IC50 values in the low micromolar range (IC50 = 0.8-24 μM). ln general, the compounds had only weak effects upon CB1, CB2, and VR1 receptors (Ki > 1000-10000 nM). In addition, there was no obvious relationship between the abilities of the compounds to affect anandamide uptake and to inhibit anandamide metabolism by fatty acid amidohydrolase (FAAH; IC50 = 30-113 μM). This indicates that the compounds do not exert their effects secondarily to FAAH inhibition. It is hoped that these compounds, particularly the most potent in this series (compound 5, UCM707, with IC50 values for anandamide uptake and FAAH of 0.8 and 30 μM, respectively), will provide useful tools for the elucidation of the role of the anandamide transporter system in vivo.
- López-Rodríguez, María L.,Viso, Alma,Ortega-Gutiérrez, Silvia,Fowler, Christopher J.,Tiger, Gunnar,De Lago, Eva,Fernández-Ruiz, Javier,Ramos, José A.
-
p. 1512 - 1522
(2007/10/03)
-
- 2-aminobenzoxazole derivatives and combinatorial libraries thereof
-
The present invention relates to novel 2-aminobenzoxazole derivative compounds of the following formula: wherein R1 to R4 and Z have the meanings provided herein. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing 2-aminobenzoxazole derivative compounds.
- -
-
-
- Benzothiazole derivatives with activity as adenosine receptor ligands
-
The present invention relates to substituted benzothiazole derivitives and to their pharmaceutically acceptable salts useful for the treatment of diseases related to the adenosine receptor.
- -
-
-
- N,N-Bis(trimethylsilyl)methoxymethylamine as a Convenient Synthetic Equivalent for +CH2NH2: Primary Aminomethylation of Organometallic Compounds
-
The introduction of the primary aminomethyl unit at carbon through N,N-bis(trimethylsilyl)aminomethylation of Grignard and organolithium compounds can be achieved in good yield using N,N-bis(trimethylsilyl)methoxymethylamine (1).
- Morimoto, Toshiaki,Takahashi, Toshio,Sekiya, Minoru
-
p. 794 - 795
(2007/10/02)
-