- The Suzuki-Miyaura cross coupling reactions on solid support. Link to solution phase directed ortho metalation. The Leznoff acetal linker approach to biaryl and heterobiaryl aldehydes
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The synthesis of the titled compounds by Suzuki-Miyaura cross coupling on Merrifield resin - Leznoff acetal - linked halo benzaldehydes followed by mild acid hydrolysis is reported; synthetic utility for heterocycles based on solution phase Directed ortho Metalation chemistry is demonstrated.
- Chamoin,Houldsworth,Kruse,Bakker, W. Iwema,Snieckus
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- Hollow nanoreactors for Pd-catalyzed Suzuki-Miyaura coupling and O-propargyl cleavage reactions in bio-relevant aqueous media
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We describe the fabrication of hollow microspheres consisting of mesoporous silica nanoshells decorated with an inner layer of palladium nanoparticles and their use as Pd-nanoreactors in aqueous media. These palladium-equipped capsules can be used to promote the uncaging of propargyl-protected phenols, as well as Suzuki-Miyaura cross-coupling, in water and at physiologically compatible temperatures. Importantly, the depropargylation reaction can be accomplished in a bioorthogonal manner in the presence of relatively high concentrations of biomolecular components and even in the presence of mammalian cells.
- Destito, Paolo,Sousa-Castillo, Ana,Couceiro, José R.,López, Fernando,Correa-Duarte, Miguel A.,Mascare?as, José L.
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- PALLADIUM-CATALYZED ARYLATION OF FURAN, THIOPHENE, BENZOFURAN AND BENZOTHIOPHENE
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Treatment of ?-electron sufficient aromatic heterocycles such as furan, thiophene, benzofuran and benzothiophene with aryl bromides in the presence of tetrakis(triphenyphosphine)palladium gave the corresponding 2-aryl aromatic heterocycles.
- Ohta, Akihiro,Akita, Yasuo,Ohkuwa, Teruya,Chiba, Mari,Fukunaga, Ryuichi,et al.
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- Unified Protocol for Fe-Based Catalyzed Biaryl Cross-Couplings between Various Aryl Electrophiles and Aryl Grignard Reagents
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The combination of commonly used FeCl3/SIPr with Ti(OEt)4/PhOM enabled a highly general iron-based catalyst system, which could efficiently catalyze the biaryl coupling reaction between various electrophiles (I, Br, Cl, OTs, OCONMe2, OSO2NMe2) and common or functionalized aryl Grignard reagents with high functional group tolerance. Selective couplings of aryl iodides and bromides over the corresponding oxygen-based electrophiles have been achieved, and thus a terphenyl acid intermediate for anidulafungin was conveniently synthesized via an orthogonal coupling strategy.
- Wang, Lei,Wei, Yi-Ming,Zhao, Yan,Duan, Xin-Fang
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- A convenient microwave assisted arylzinc generation-Negishi coupling protocol
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Arylzinc reagents were readily prepared from aryl iodides using a Zn-Cu couple in a microwave environment. A sequential arylzinc formation-Negishi cross-coupling protocol suitable for parallel high-throughput synthesis has been developed.
- Mutule, Ilga,Suna, Edgars
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- 2-Arylthienyl-substituted 1,3-benzothiazoles as new nonlinear optical chromophores
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A series of nonlinear optical chromophores 6 containing a substituted benzothiazole ring have been synthesized and characterized. 1,3-Benzothiazoles 6 were prepared by treating various formyl derivatives of thienyl compounds with ortho-aminobenzenethiol i
- Costa, Susana P. G.,Batista, Rosa M. F.,Cardoso, Paulo,Belsley, Michael,Raposo, Maria Manuela M.
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- 5-(Naphth-1-yl)- and 5-[(1,1'-biphenyl)-4-yl]isoxazole-3-carbaldehyde oximes: Synthesis, complexes with palladium, and application in catalysis
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1-(Naphth-1-yl)- and 1-[(1,1'-biphenyl)-4-yl-3,4,4-trichloro-3-buten-1-ones were synthesized by acylation of naphthalene and biphenyl with 3,4,4-trichloro-3-butenoyl chloride. Further reaction with hydroxylamine led to 5-(naphth-1-yl)- and 5-[(1,1'-biphen
- Potkin,Bumagin,Zelenkovskii,Petkevich,Livantsov,Golantsov
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- Effective bimetallic composite catalysts for the synthesis of arylated furans and thiophenes in aqueous media
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[Figure not available: see fulltext.] N-(4,6-Dimethylpyrimidin-2-yl)-5-phenylisoxazole-3-carboxamide was used as a ligand for obtaining bimetallic boron-containing heterogeneous catalysts Pd–Ni(Co)–B–L (Ni(Co):Pd = 9:1). The obtained composites were highl
- Bumagin, Nikolay A.,Petkevich, Sergey K.,Kletskov, Alexey V.,Alekseyev, Roman S.,Potkin, Vladimir I.
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- High-turnover aminopyridine-based Pd-catalysts for Suzuki-Miyaura reaction in aqueous media
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A high-turnover catalytic system based on commercially available aminopyridines (L) and PdCl2 has been developed for Suzuki-Miyaura reaction in aqueous media. Reactions of arylboronic acids with a wide range of aryl iodides, bromides and chlorides proceeded in the presence of these catalysts for a short time in aqueous media to afford the cross-coupling products in high yields. Furthermore, this protocol allows tolerating a wide range of functional groups.
- Bumagin, Nikolay A.
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- Photo-oxidative Cross-Dehydrogenative Coupling-Type Reaction of Thiophenes with α-Position of Carbonyls Using a Catalytic Amount of Molecular Iodine
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A metal-free photo-oxidative intermolecular C-H/C-H coupling reaction of thiophenes is demonstrated with carbonyls using a catalytic amount of molecular iodine. In this system, molecular oxygen in the air acted as a terminal oxidant to regenerate molecular iodine. A mechanistic study was also performed.
- Sudo, Yusuke,Yamaguchi, Eiji,Itoh, Akichika
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- An effective activation of palladium phosphine complexes in aqueous phase reactions of hetero-aromatic boronic acids with aryl halides
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We have developed a simple and effective method for the activation of palladium phosphine complexes in the Suzuki reaction (TON up to 9800, TOF up to 58800 h-1) by selecting an aqueous reaction medium instead of organic solvents. This method wa
- Bumagin,Veselov,Belov
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- Sterically hindered N-aryl/benzyl substituted piperidoimidazolin-2-ylidene palladium complexes and their catalytic activities
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A series of N-aryl (2a,b) or benzyl (2c,d) substituted piperidoimidazolinium salts and their palladium complexes (3a-d) were prepared and characterized by 1H, 13C NMR, IR spectroscopy and elemental analysis. The crystal structures of 3a and 3c have been determined by X-ray crystallography. Thermogravimetric analysis (TGA) was applied to complexes (3a–d). The palladium complexes have been employed as catalyst for Suzuki-Miyaura cross coupling. The N-aryl substituted complex 3b was a highly efficient precatalyst and successfully employed in Suzuki-Miyaura cross coupling reactions of (hetero)aryl chlorides with arylboronic acids in air. In addition, the oxidative addition step of the reaction mechanism involving chlorobenzene and the catalysts 3a, 3b, 3c and 3d were computationally investigated by the DFT-ω-B97X-D method and complete agreement were obtained with the catalytic results. To measure σ-donating and π-acceptor properties of the new ligands, the rhodium carbonyl complexes were also prepared.
- Gacal, Elif,Denizalt?, Serpil,K?nal, Arma?an,G?k?e, Ayta? Gürhan,Türkmen, Hayati
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- Gold Catalysts Can Generate Nitrone Intermediates from a Nitrosoarene/Alkene Mixture, Enabling Two Distinct Catalytic Reactions: A Nitroso-Activated Cycloheptatriene/Benzylidene Rearrangement
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Gold-catalyzed reactions of cycloheptatrienes with nitrosoarenes yield nitrone derivatives efficiently. This reaction sequence enables us to develop gold-catalyzed aerobic oxidations of cycloheptatrienes to afford benzaldehyde derivatives using CuCl and nitrosoarenes as co-catalysts (10-30 mol %). Our density functional theory calculations support a novel nitroso-activated rearrangement, tropylium → benzylidene. With the same nitrosoarenes, we developed their gold-catalyzed [2 + 2 + 1]-annulations between nitrosobenzene and two enol ethers to yield 5-alkoxyisoxazolidines using 1,4-cyclohexadienes as hydrogen donors.
- Cheng, Mu-Jeng,Kardile, Rahul Dadabhau,Kuo, Tung-Chun,Liu, Rai-Shung,More, Sayaji Arjun
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supporting information
p. 5506 - 5511
(2021/07/31)
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- EIF4E INHIBITORS AND USES THEREOF
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The present invention provides compounds inhibiting elF4E activity and compositions and methods of using thereof.
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Paragraph 00630; 00639
(2021/09/11)
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- Aerobic Cu and amine free Sonogashira and Stille couplings of aryl bromides/chlorides with a magnetically recoverable Fe3O4@SiO2 immobilized Pd(II)-thioether containing NHC
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Two value added C–C cross coupling reactions; Sonogashira and Stille couplings were achieved at milder conditions in the catalytic presence of a magnetically recoverable heterogeneous catalyst Fe3O4@SiO2@NHC^SPh-Pd(II). The catalyst was earlier reported for Suzuki-Miyaura reaction, and as an extension of its catalytic efficiency, the Stille and Sonogashira cross coupling reactions under aerobic condition has been explored in present report. The Sonogashira coupling of aryl bromides and terminal alkynes produced an excellent yield (~96% at 0.25 mol% Pd) of the desired coupling product under copper and amines free conditions. Moreover, an excellent Stille coupling of readily available and more latent aryl chlorides and trialkylstannane was obtained (yields up to 95% at 0.25 mol% Pd) in absence of toxic fluorides additives. The broad substrate scope of the catalyst for both the coupling reactions and the magnetically recoverable feature of catalyst make this reaction highly desirable for industrial applications of present heterogeneous catalysis.
- Khandaka, Himanshu,Sharma, Kamal Nayan,Joshi, Raj Kumar
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supporting information
(2021/02/20)
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- Schiff base multifunctional fluorescent probe as well as preparation method and application thereof
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The invention belongs to the technical field of chemical analysis, and particularly relates to a Schiff base multifunctional fluorescent probe and a preparation method and application thereof, which can be used for simultaneously detecting copper ions, zinc ions and aluminum ions. The preparation method comprises the following steps: carrying out Suzuki reaction on 2-bromothiophene and p-formylphenylboronic acid according to a certain ratio under certain conditions to obtain an intermediate 4-(2-thienyl)benzaldehyde, and carrying out aldehyde-amine condensation reaction on the intermediate ando-aminophenol in absolute ethyl alcohol to obtain the target product. The probe is a Schiff base compound, has imine bonds and hydroxyl groups, and has excellent selectivity on copper ions, zinc ionsand aluminum ions: in an acetonitrile solution system, the probe shows blue fluorescence turn-on for the copper ions; meanwhile, in an approximate aqueous solution system, the probe shows orange fluorescence turn-on for zinc ions and shows blue fluorescence turn-on for aluminum ions. In addition, the probe basically has no change in fluorescence signals when acting with other common metal ions, has strong anti-interference capability, good sensing property and low detection limit, and has certain application potential in the aspect of environmental metal ion detection.
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Paragraph 0039; 0046-0048
(2021/03/13)
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- BENZIMIDAZOLE COMPOUNDS AND USE THEREOF FOR TREATING ALZHEIMER'S DISEASE OR HUNTINGTON'S DISEASE
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Benzimidazole compounds of formula (I), shown below, are disclosed. The compounds are potent human glutaminyl cyclase inhibitors. Also disclosed is a pharmaceutical composition containing one of these compounds and a pharmaceutical acceptable carrier, as well as a method of treating Alzheimer's disease or Huntington's disease by administering to a subject in need thereof an effective amount of such a compound.
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Page/Page column 13; 17; 18; 50
(2020/03/23)
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- BENZIMIDAZOLE COMPOUNDS AND USE THEREOF FOR TREATING ALZHEIMER'S DISEASE OR HUNTINGTON'S DISEASE
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Benzimidazole compounds of formula (I), shown below, are disclosed. The compounds are potent human glutaminyl cyclase inhibitors. Also disclosed is a pharmaceutical composition containing one of these compounds and a pharmaceutical acceptable carrier, as well as a method of treating Alzheimer's disease or Huntington's disease by administering to a subject in need thereof an effective amount of such a compound.
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Paragraph 0038; 0044; 0163-0164
(2020/03/23)
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- Synthesis of Substituted Benzaldehydes via a Two-Step, One-Pot Reduction/Cross-Coupling Procedure
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The synthesis of functionalized (benz)aldehydes, via a two-step, one-pot procedure, is presented. The method employs a stable aluminum hemiaminal as a tetrahedral intermediate, protecting a latent aldehyde, making it suitable for subsequent cross-coupling with (strong nucleophilic) organometallic reagents, leading to a variety of alkyl and aryl substituted benzaldehydes. This very fast methodology also facilitates the effective synthesis of a 11C radiolabeled aldehyde. Aluminum-ate complexes enable transmetalation of alkyl fragments onto palladium and subsequent cross-coupling.
- Heijnen, Dorus,Helbert, Hugo,Luurtsema, Gert,Elsinga, Philip H.,Feringa, Ben L.
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supporting information
p. 4087 - 4091
(2019/06/14)
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- Barbituric acid derivative of monosubtstituted five-membered heterocycle and preparation method thereof
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The invention discloses a barbituric acid derivative of monosubtstituted five-membered heterocycle and a preparation method thereof. The chemical structural formula of the barbituric acid derivative is shown in the specification. The barbituric acid derivative based on thiophene or furan is synthesized for the first time, and it is found through an experiment that the derivative shows a solvationcolor change effect: along with increase of the solvent polarity, a fluorescence spectrum is in red shift.
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Paragraph 0040; 0056-0058; 0062
(2018/10/19)
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- Optimization of N-Substituted Oseltamivir Derivatives as Potent Inhibitors of Group-1 and -2 Influenza A Neuraminidases, Including a Drug-Resistant Variant
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On the basis of our earlier discovery of N1-selective inhibitors, the 150-cavity of influenza virus neuraminidases (NAs) could be further exploited to yield more potent oseltamivir derivatives. Among the synthesized compounds, 15b and 15c were exceptionally active against both group-1 and -2 NAs. Especially for 09N1, N2, N6, and N9 subtypes, they showed 6.80-12.47 and 1.20-3.94 times greater activity than oseltamivir carboxylate (OSC). They also showed greater inhibitory activity than OSC toward H274Y and E119V variant. In cellular assays, they exhibited greater potency than OSC toward H5N1, H5N2, H5N6, and H5N8 viruses. 15b demonstrated high metabolic stability, low cytotoxicity in vitro, and low acute toxicity in mice. Computational modeling and molecular dynamics studies provided insights into the role of R group of 15b in improving potency toward group-1 and -2 NAs. We believe the successful exploitation of the 150-cavity of NAs represents an important breakthrough in the development of more potent anti-influenza agents.
- Zhang, Jian,Poongavanam, Vasanthanathan,Kang, Dongwei,Bertagnin, Chiara,Lu, Huamei,Kong, Xiujie,Ju, Han,Lu, Xueyi,Gao, Ping,Tian, Ye,Jia, Haiyong,Desta, Samuel,Ding, Xiao,Sun, Lin,Fang, Zengjun,Huang, Boshi,Liang, Xuewu,Jia, Ruifang,Ma, Xiuli,Xu, Wenfang,Murugan, Natarajan Arul,Loregian, Arianna,Huang, Bing,Zhan, Peng,Liu, Xinyong
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p. 6379 - 6397
(2018/07/15)
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- End-Capping Groups for Small-Molecule Organic Semiconducting Materials: Synthetic Investigation and Photovoltaic Applications through Direct C–H (Hetero)arylation
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A Pd-catalyzed C–H (hetero)arylation methodology has been optimized for the efficient synthesis of various useful end-capping groups that are widely applied in small-molecule optoelectronic materials. We report herein the synthesis of a broad scope of target molecules ranging from donor-type through acceptor-type to hybrid-type end-capping groups. To demonstrate their application in dye-sensitized solar cells, we have designed two new D–A–π–A′-type organic sensitizers (CYL-3 and CYL-4), which were synthesized in a step-economic manner by sequential C–H arylations using the facilely obtained end-capping groups. The devices based on CYL-3 and CYL-4 give Vocvalues of 0.67–0.71 V, Jscvalues of 10.07–11.63 mA cm–2, and FF values of 70.6–72.9 %, which correspond to overall power conversion efficiencies of 4.76–6.02 %. This work is expected to become a practical synthetic alternative allowing materials scientists to access small-molecule organic materials in fewer synthetic transformations.
- Lu, Te-Jui,Lin, Po-Han,Lee, Kun-Mu,Liu, Ching-Yuan
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p. 111 - 123
(2017/01/14)
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- Antimalarials with benzothiophene moieties as aminoquinoline partners
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Malaria is a severe and life-threatening disease caused by Plasmodium parasites that are spread to humans through bites of infected Anopheles mosquitoes. Here, we report on the efficacy of aminoquinolines coupled to benzothiophene and thiophene rings in inhibiting Plasmodium falciparum parasite growth. Synthesized compounds were evaluated for their antimalarial activity and toxicity, in vitro and in mice. Benzothiophenes presented in this paper showed improved activities against a chloroquine susceptible (CQS) strain, with potencies of IC50 = 6 nM, and cured 5/5 Plasmodium berghei infected mice when dosed orally at 160 mg/kg/day x 3 days. In the benzothiophene series, the examined antiplasmodials were more active against the CQS strain D6, than against strains chloroquine resistant (CQR) W2 and multidrug-resistant (MDR) TM91C235. For the thiophene series, a very interesting feature was revealed: hypersensitivity to the CQR strains, resistance index (RI) of 1. This is in sharp contrast to chloroquine, indicating that further development of the series would provide us with more potent antimalarials against CQR strains.
- Konstantinovi?, Jelena,Videnovi?, Milica,Srbljanovi?, Jelena,Djurkovi?-Djakovi?, Olgica,Bogojevi?, Katarina,Sciotti, Richard,?olaja, Bogdan
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supporting information
(2017/03/11)
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- Novel compound and solar cell including the same
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The present invention relates to a novel compound and a solar cell including the same. The novel compound according to the present invention can realize various efficiencies by replacing metal dyes, which are used as dye compounds of solar cells at low co
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Paragraph 0206
(2017/12/09)
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- Cobalt-Catalyzed Biaryl Couplings via C-F Bond Activation in the Absence of Phosphine or NHC Ligands
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A highly general and selective Co-catalyzed biaryl coupling through C-F cleavage under phosphine or NHC-free conditions was described. A broad range of aryl fluorides including unactivated fluorides as well as those with sensitive functionalities could couple with various Ti(OEt)4-mediated aryl Grignard reagents with high selectivity under the catalysis of CoCl2/DMPU. Importantly, selective C-F bond activation couplings between two types of fluorines (difluorinated aromatics and on two different coupling partners) and in the presence of C-Cl or C-Br bonds could also be achieved.
- Wei, Juan,Liu, Kun-Ming,Duan, Xin-Fang
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p. 1291 - 1300
(2017/02/10)
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- VP1 crystal structure-guided exploration and optimization of 4,5-dimethoxybenzene-based inhibitors of rhinovirus 14 infection
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Human rhinoviruses (HRV) are the predominant cause of common colds and flu-like illnesses, but are also responsible for virus-induced exacerbations of asthma and chronic obstructive pulmonary disease. However, to date, no drug has been approved yet for clinical use. In this study, we present the results of the structure-based lead optimization of a class of new small-molecule inhibitors that we previously reported to bind into the pocket beneath the canyon of the VP1 protein. A small series of analogues that we designed based on the available structure and interaction data were synthesized and evaluated for their potency to inhibit the replication of HRV serotype 14. 2-(4,5-Dimethoxy-2-nitrophenyl)-1-(4-(pyridin-4-yl)phenyl)ethanol (3v) was found to be a potent inhibitor exhibiting micromolar activity (EC50 Combining double low line 3.4 ± 1.0 μM) with a toxicity for HeLa cells that was significantly lower than that of our previous hit (LPCRW-0005, CC50 Combining double low line 104.0 ± 22.2 μM; 3v, CC50 > 263 μM).
- Da Costa, Laurène,Roche, Manon,Scheers, Els,Coluccia, Antonio,Neyts, Johan,Terme, Thierry,Leyssen, Pieter,Silvestri, Romano,Vanelle, Patrice
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p. 453 - 462
(2016/04/19)
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- Iron-catalyzed oxidative biaryl cross-couplings via mixed diaryl titanates: Significant influence of the order of combining aryl Grignard reagents with titanate
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The mixed diaryl titanates were used for the first time to modify the reactivity of two aryl Grignard reagents. Two titanate intermediates, Ar[Ar′Ti(OR)3]MgX and Ar′[ArTi(OR)3]MgX, formed via alternating the sequence of combining Grignard reagents with ClTi(OR)3 showed a significant reactivity difference. Taking advantage of such different reactivity, two highly structurally similar aryl groups could be facilely assembled through iron-catalyzed oxidative cross-couplings using oxygen as the oxidant. This journal is
- Liu, Kun Ming,Wei, Juan,Duan, Xin Fang
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supporting information
p. 4656 - 4658
(2015/05/27)
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- Palladacycles derived from arylphosphinamides for mild Suzuki-Miyaura cross-couplings
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We present a type of palladacyclic complexes derived from arylphosphinamides which can be used as efficient and versatile precatalysts for mild Suzuki-Miyaura cross-coupling. With the presence of 1.0 mol% of palladacycles, a wide variety of aryl bromides and boronic acids could be coupled very efficiently at ambient temperature and under air atmosphere without the need of external supporting ligands. Moreover, the mild conditions also allow for smooth coupling of electron-deficient, i.e., the less stable aryl triflates. In addition to the highly catalytic activity, the palladacyclic complexes can be very easily prepared through a two-step procedure from the readily affordable diphenyl-phosphinic chloride and exhibit excellent stability toward air and moisture. Due to these prominent properties, the new palladacycles would find practical use in Suzuki-Miyaura couplings.
- Wu, Guo-Jie,Han, Fu-She,Zhao, Yu-Long
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p. 69776 - 69781
(2015/09/01)
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- Discovery of N-substituted oseltamivir derivatives as potent and selective inhibitors of H5N1 influenza neuraminidase
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To discover group-1-specific neuraminidase (NA) inhibitors that are especially involved in combating the H5N1 virus, two series of oseltamivir derivatives were designed and synthesized by targeting the 150-cavity. Among these, compound 20l was the most potent N1-selective inhibitor, with IC50 values of 0.0019, 0.0038, and 0.0067 μM against NAs from three H5N1 viruses. These values are better than those of oseltamivir carboxylate. Compound 32 was another potent N1-selective inhibitor that exhibited a 12-fold increase in activity against the H274Y mutant relative to oseltamivir carboxylate. Molecular docking studies revealed that the 150-cavity was an auxiliary binding site that may contribute to the high selectivity of these compounds. The present work is a significant breakthrough in the discovery of potent group-1-specific neuraminidase inhibitors, which may be further investigated for the treatment of infection by the H5N1 virus.
- Xie, Yuanchao,Xu, Dongqing,Huang, Bing,Ma, Xiuli,Qi, Wenbao,Shi, Fangyuan,Liu, Xinyong,Zhang, Yingjie,Xu, Wenfang
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p. 8445 - 8458
(2014/12/10)
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- Fluorine-thiophene-substituted organic dyes for dye sensitized solar cells
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Novel triphenylamine (TPA)-based organic dyes were synthesized and assessed for their performance in dye-sensitized solar cells (DSSCs). In the dyes considered the TPA group and the cyanoacetic acid have the role of electron-donor and -acceptor, respectively, whereas a thienyl-fluoro-phenyl- substituted was introduced as π-linker to improve the dye performance in DSSCs. Experimental characterizations empasize that the presence of electron withdrawing substituents in the linker close to the electron-acceptor moiety leads to a more efficient intramolecular photoinduced charge transfer. In fact, photovoltaic experiments reveal that the DSSCs based on the thienyl-o-fluoro- phenyl substituted dyes yield a better solar-energy-to-electricity conversion efficiency.
- Scrascia, Angela,De Marco, Luisa,Laricchia, Savio,Picca, Rosaria Anna,Carlucci, Claudia,Fabiano, Eduardo,Capodilupo, Agostina Lina,Della Sala, Fabio,Gigli, Giuseppe,Ciccarella, Giuseppe
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p. 11909 - 11921
(2013/09/24)
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- Room-temperature Suzuki-Miyaura coupling of heteroaryl chlorides and tosylates
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Suzuki-Miyaura coupling of heteroaryls is an important method for the preparation of compound libraries for medicinal chemistry and materials research. Although many catalysts have been developed, none of them have been generally applicable to the coupling reactions of heteroaryl chlorides and tosylates at room temperature. We discovered that a catalyst combination of Pd(OAc)2 and XPhos (2-dicyclohexylphosphanyl-2',4',6'- triisopropylbiphenyl) could efficiently catalyze these couplings. Besides the choice of catalyst, the use of hydroxide bases in an aqueous alcoholic solvent was essential for fast couplings. These conditions promoted fast release of active catalyst (XPhos)Pd0, and accelerated the transmetalation in the catalytic cycle. Most of the major families of heteroaryl chlorides (31 examples) and tosylates (17 examples) reached full conversion within minutes to hours at room temperature. The method could be easily scaled up for gram-scale synthesis. Furthermore, we examined the relative reactivity of coupling partners in whole reactions. Electron-rich heteroaryl chlorides and tosylates reacted more slowly than electron-deficient ones, in the order of indole, pyrrole furan, thiophene > pyridine. Similarly, electron-deficient arylboronic acids were less reactive than electron-neutral and electron-rich ones. The reactivity trends from this study can help to choose appropriate coupling partners for Suzuki reactions.
- Yang, Junfeng,Liu, Sijia,Zheng, Jian-Feng,Zhou, Jianrong
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supporting information
p. 6248 - 6259,12
(2020/09/16)
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- Sequential Suzuki/asymmetric aldol and Suzuki/Knoevenagel reactions under aqueous conditions
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Here we describe for the first time a sequential Suzuki/asymmetric aldol reaction. Such sequential approach was achieved through the combined use of an ionic liquid supported palladium catalyst and the organocatalyst trans-4-(2,2-diphenylacetoxy)proline. Suzuki and asymmetric aldol reactions were performed under aqueous conditions. The use of a palladium catalyst under basic conditions allowed also the first example of sequential Suzuki/Knoevenagel reaction. Reactions were carried out under aqueous conditions and products were isolated in good to high yields and, in the case of the Suzuki/aldol reaction, with diastereoselectivities up to 91:9 and enantioselectivities up to at least 99%.
- Gruttadauria, Michelangelo,Bivona, Lucia Anna,Lo Meo, Paolo,Riela, Serena,Noto, Renato
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experimental part
p. 2635 - 2642
(2012/06/04)
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- Pyrazole[3,4-e][1,4]thiazepin-7-one derivatives as a novel class of Farnesoid X Receptor (FXR) agonists
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A virtual screening procedure was applied to the discovery of structurally diverse non-steroidal Farnesoid X Receptor (FXR) agonists. From 117 compounds selected by virtual screening, a total of 47 compounds were found to be FXR agonists, with 34 of them showing activity below a concentration of 20 μM. 1H-Pyrazole[3,4-e][1,4]thiazepin-7-one-based hit compound 7 was chosen for hit-to-lead optimization. A large number of 1H-pyrazole[3,4-e][1,4]thiazepin-7- one derivatives was designed, synthesized, and evaluated by a cell-based luciferase transactivation assay for their agonistic activity against FXR. Most of them exhibited low micromolar range of potency and very high efficacy.
- Marinozzi, Maura,Carotti, Andrea,Sansone, Emanuele,MacChiarulo, Antonio,Rosatelli, Emiliano,Sardella, Roccaldo,Natalini, Benedetto,Rizzo, Giovanni,Adorini, Luciano,Passeri, Daniela,De Franco, Francesca,Pruzanski, Mark,Pellicciari, Roberto
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supporting information; experimental part
p. 3429 - 3445
(2012/07/30)
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- Palladium-catalyzed direct arylation of heteroaromatic compounds: Improved conditions utilizing controlled microwave heating
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A versatile and rapid microwave-assisted procedure for the palladium-catalyzed direct arylation of heterocycles by aryl bromides and heteroaryl bromides is described. This novel protocol features short coupling times (10-60 min) and low catalyst loadings
- Baghbanzadeh, Mostafa,Pilger, Christian,Oliver Kappe
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experimental part
p. 8138 - 8142
(2011/11/07)
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- Direct 2-arylation of thiophene using low loading of a phosphine-free palladium catalyst
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The direct coupling of aryl halides with thiophene would be a considerable advantage for sustainable development because of only HBr associated with a base as by-product is formed and the number of steps to prepare these compounds is less than in more cla
- Bensaid, Souhila,Roger, Julien,Beydoun, Kassem,Roy, David,Doucet, Henri
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experimental part
p. 3524 - 3531
(2011/09/16)
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- Ionic liquid supported organotin reagents: Green tools for stille cross-coupling reactions with brominated substrates
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Efficiency of ionic liquid supported organotin reagents in Stille cross-coupling reactions involving aryl bromides has been investigated. In a general manner, products were isolated with good yields by using a very simple catalytic system without the need of solvent, ligand, or additives. The organotin compounds were recycled without loss of activity and the contamination by tin was limited and controlled ([Sn] 3 ppm). Clean tin's good! Efficiency of ionic liquid supported organotin reagents in Stille cross-coupling reactions involving aryl bromides has been investigated. Products were isolated with good yields by using a verysimple catalytic system. Organotin compounds were recycled without loss of activity and the contamination by tin was limited ([Sn] 3 ppm).
- Louaisil, Nicolas,Pham, Phuoc Dien,Boeda, Fabien,Faye, Djibril,Castanet, Anne-Sophie,Legoupy, Stephanie
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supporting information; experimental part
p. 143 - 149
(2011/03/18)
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- Synthesis and photovoltaic properties of new metalloporphyrin-containing polyplatinyne polymers
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Three new solution-processable platinum(II) polyyne polymers containing zinc(II) porphyrinate chromophores P1, P2, and P3 and their corresponding dinuclear model complexes were synthesized via the CuI-catalyzed dehydrohalogenation reaction of the platinum(II) chloride precursor and each of the respective bis(ethynyl)-zinc(porphyrin) metalloligands. The thermal, photophysical (absorption, excitation and emission spectra), electrochemical, and photovoltaic properties of P1-P3 were investigated. These results are also correlated by time-dependent density functional theory (TDDFT) calculations. The computations corroborate the presence of moderate conjugation in the π-systems, somewhat more accentuated for P3 where more favorable dihedral angles between the porphyrin and thiophene rings are noted. Moreover, the computed excited states are predicted to be π-π* in nature with some charge transfer components from the trans-[-C≡CPt(L)2C≡ C-]n unit to the porphyrin rings. The optical bandgaps range from 1.93 to 2.02 eV for P1-P3. Intense π-π*-localized fluorescence emissions typical of the Q-bands of the polymers were observed. The effect of thiophene ring along the polymer chain on the extent of π-conjugation, luminescent and photovoltaic properties of these metalated materials was also examined. Bulk heterojunction solar cells using these metallopolymers as an electron donor blended with a methanofullerene electron acceptor were studied. In one case, the metallopolymer P3 showed a power conversion efficiency of 1.04% with the open-circuit voltage of 0.77 V, short-circuit current density of 3.42 mA cm-2 and fill factor of 0.39 under illumination of an AM 1.5 solar cell simulator.
- Zhan, Hongmei,Lamare, Simon,Ng, Annie,Kenny, Tommy,Guernon, Hannah,Chan, Wai-Kin,Djurisic, Aleksandra B.,Harvey, Pierre D.,Wong, Wai-Yeung
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scheme or table
p. 5155 - 5167
(2012/04/17)
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- Benzimidazolium-pyrazole-palladium(II) complexes: New and efficient catalysts for Suzuki, Heck and Sonogashira reactions
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Three unsymmetrical benzimidazoliumpyrazole N-N ligands 2-(1-propylbenzimidazolylmethyl)-3,5-di-R-pyrazole (R=H, Me, t-Bu) have been conveniently prepared and structurally analyzed. The solid lattice packingof the R=Me compound at 223 K reveals one-dimensional "zig-zag" water chains stabilized by organic molecular channels through N...H-O and O-H...O bonding. These hybrid ligands add to palladium(II) to give high yields of air-stable complexes that are fully characterized by NMR, ESI, and X-ray single-crystal crystallography. They are active Suzuki catalysts at room temperature towards cross-couplingof unactivated aryl bromides and 5- or 6-membered heteroaryl bromides with arylboronic acids with turnover frequencies (TOF) reachingas high as 60,000 h-1. Their catalytic efficiency is significantly better than that of the C-N carbene-imidazole analogue. These catalysts are also active in Heck and Sonogashira cross-coupling reactions of aryl bromides giving the desired products in good yields. These results suggested that these Pd(II) complexes with N-based hybrid ligands are versatile and efficient catalysts for different types of cross-couplingreactio ns under aerobic conditions.
- Li, Fuwei,Hor, T. S. Andy
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experimental part
p. 2391 - 2400
(2009/10/08)
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- Improved preparative method for 1,2-diaryl-3,4-diphosphinidenecyclobutenes and its application to the studies of l,2-bis(arylthienyl)-3,4- diphosphinidenecyclobutenes
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Sterically protected 1,2-diary1-3,4-diphosphinidenecyclobutenes were prepared from 3-ary1-2-bromo-1-(2,4,6-tri-t-butylphenyl)-3-(trimethylsiloxy)- l-phosphapropene using t-butyllithium and 1,2-dibromoethane, and the properties of the products, such as 1,2
- Toyota, Kozo,Horikawa, Keiko,Jensen, Rader S.,Omori, Kouhei,Kawasaki, Subaru,Ito, Shigekazu,Yoshifuji, Masaaki,Morita, Noboru
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body text
p. 1580 - 1586
(2009/07/18)
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- PIPERIDINES USEFUL FOR THE TREATMENT OF CENTRAL NERVOUS SYSTEM DISORDERS
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The invention relates to compounds which are substituted chiral or achiral derivatives of 3- or 4- aminopiperidine of the general formula (I). The invention also concerns related aspects including processes for the preparation of the compounds, pharmaceutical compositions containing one or more compounds of general formula I and especially their use as inhibitors of β-secretases.
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- SUBSTITUTED 3- AND 4- AMINOMETHYLPIPERIDINES FOR USE AS BETA-SECRETASE IN THE TREATMENT OF ALZHEIMER’S DISEASE
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The invention relates to novel compounds, which are substituted chiral or achiral derivatives of 3- or 4- aminomethylpiperidine of the general formula (I). The invention also concerns related aspects including processes for the preparation of the compounds, pharmaceutical compositions containing one or more compounds of general formula (I) and especially their use as inhibitors of beta-secretases for the treatment of Alzheimer’s disease.
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Page/Page column 48
(2008/06/13)
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- Generation of aryl radicals from arylboronic acids by manganese(III) acetate: Synthesis of biaryls and heterobiaryls
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The efficient generation of aryl radicals from arylboronic acids by manganese(III) acetate is described. In aromatic solvents, in situ generated aryl radicals afford the corresponding biaryls in very good yields. This method works selectively, and yields
- Demir, Ayhan S.,Reis, Oemer,Emrullahoglu, Mustafa
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p. 578 - 580
(2007/10/03)
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- Design of selective peptidomimetic agonists for the human orphan receptor BRS-3
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New tool substances may help to unravel the physiological role of the human orphan receptor BRS-3 and its possible use as a drug target for the treatment of obesity and cancer. In continuation of our work on BRS-3, the solid- and solution-phase synthesis of a library of low molecular weight peptidomimetic agonists based on the recently developed short peptide agonist 4 is described. Functional potencies of the compounds were determined measuring calcium mobilization in a fluorometric imaging plate reader (FLIPR) assay. Focusing on the N-terminus, the D-Phe-Gln moiety of 4 was modified in a combinatorial SAR-oriented medicinal chemistry approach. With the incorporation of N-arylated glycine and alanine building blocks azaglycine, piperazine, or piperidine and the synthesis of semicarbazides and semicarbazones, a number of highly potent and selective compounds with a reduced number of peptide bonds were obtained, which also should have enhanced metabolic stability.
- Weber, Dirk,Berger, Claudia,Eickelmann, Peter,Antel, Jochen,Kessler, Horst
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p. 1918 - 1930
(2007/10/03)
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- ANTIVIRALLY ACTIVE HETEROCYCLIC AZAHEXANE DERIVATIVES
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There are described compounds of formula I*, STR1 wherein R. sub.1 is lower alkoxycarbonyl,R 2 is secondary or tertiary lower alkyl or lower alkylthio-lower alkyl, R. sub.3 is phenyl that is unsubstituted or substituted by one or more lower alkoxy radicals, or C 4-C 8 cycloalkyl,R. sub.4 is phenyl or cyclohexyl each substituted in the 4-position by unsaturated heterocyclyl that is bonded by way of a ring carbon atom, has from 5 to 8 ring atoms, contains from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, sulfinyl (--SO--) and sulfonyl (--SO 2--) and is unsubstituted or substituted by lower alkyl or by phenyl-lower alkyl,R 5, independently of R 2, has one of the meanings mentioned for R 2, andR 6, independently of R. sub.1, is lower alkoxycarbonyl,or salts thereof, provided that at least one salt-forming group is present. The compounds are inhibitors of retroviral aspartate protease and can be used, for example, in the treatment of AIDS. They exhibit outstanding pharmacodynamic properties.
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- Inhibitors of acyl-coA:cholesterol O-acyltransferase. 2. Identification and structure-activity relationships of a novel series of N-alkyl-N- (heteroaryl-substituted benzyl)-N'-arylureas
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A series of N-alkyl-N-(heteroaryl-substituted benzyl)-N'-arylurea and related derivatives represented by 2 and 3 have been prepared and evaluated for their ability to inhibit acyl-CoA:cholesterol O-acyltransferase in vitro and to lower plasma cholesterol levels in cholesterol-fed rats in vivo. Among these novel compounds, the type 3 series was superior. A pyrazol-3-yl group on the N-benzyl group of this trisubstituted urea (i.e. 3, Ar1 = pyrazol-3- yl) was identified as a heteroaromatic ring providing a good profile of biological activity. As a result of optimization of the combination with the N-alkyl group (R) and N-aryl group (At3), compound 3aq (FR186054) was identified as a new, orally efficacious ACAT inhibitor, which exhibited potent in vitro ACAT inhibitory activity (rabbit intestinal microsomes IC50 = 99 nM) and excellent hypocholesterolemic effects in cholesterol-fed rats, irrespective of administration mode (ED50 = 0.046 mg/kg dosed via the diet, ED50 = 0.44 mg/kg administered by gavage in PEG400 vehicle). Moreover, a toxicological study revealed compound 3aq to be nontoxic to the adrenal glands of dogs when tested at a single dose of 10 mg/kg po.
- Tanaka, Akira,Terasawa, Takeshi,Hagihara, Hiroyuki,Sakuma, Yuri,Ishibe, Noriko,Sawada, Masae,Takasugi, Hisashi,Tanaka, Hirokazu
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p. 2390 - 2410
(2007/10/03)
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