- Design, synthesis and biological evaluation of new imidazo[1,2-a]pyridine derivatives as selective COX-2 inhibitors
-
Three new series of methylsulfonyl-containing imidazo[1,2-a]pyridines 8a-d, 9a-d and 10a-d were designed and synthesized. Characterization of the chemical structure of these new compounds was performed using spectral and elemental analyses. The synthesized derivatives were tested for their ability to inhibit COX-1 and COX-2 isozymes in addition to their in vivo anti-inflammatory activity. The pyrazoline derivative 9a possessed the highest selectivity index among all compounds regarding COX-2 isozyme (SI = 39) and was almost three folds higher than celecoxib (SI = 13.76) with good in vivo anti-inflammatory activity (% edema inhibition = 11.16–32.64). Compound 10c showed the highest inhibitory activity towards COX-2 isozyme (IC50 = 1.06 μM) and it was the most potent anti-inflammatory derivative (% edema inhibition = 15.04–42.35) with ED50 value of 69.46 μmol/Kg which was approximately one and a half fold more potent than celecoxib (ED50 = 104.88 μmol/Kg). Also, the most potent anti-inflammatory compounds 9a, 9d, 10c and 10d were subjected to ulcerogenic liability and histopathological examinations. Compounds 9d and 10c showed ulcerogenic liability (% ulcerated area = 0.07 and 0.01, respectively) and histopathological changes close to celecoxib. Finally, molecular docking and computational prediction of physicochemical parameters were performed for the prepared compounds to support the biological results.
- Abdel-Rahman, Hamdy M.,Ali, Mohammed R. A.,Amin, Noha H.,Elsaadi, Mohammed T.,Ismael, Ahmed S.
-
-
- Development of Trifluoromethanesulfonic Acid-Immobilized Nitrogen-Doped Carbon-Incarcerated Niobia Nanoparticle Catalysts for Friedel-Crafts Acylation
-
Heterogeneous trifluoromethanesulfonic acid-immobilized nitrogen-doped carbon-incarcerated niobia nanoparticle catalysts (NCI-Nb-TfOH) that show excellent catalytic performance with low niobium loading (1 mol %) in Friedel-Crafts acylation have been developed. These catalysts exhibit higher activity and higher tolerance to catalytic poisons compared with the previously reported TfOH-treated NCI-Ti catalysts, leading to a broader substrate scope. The catalysts were characterized via spectroscopic and microscopic studies.
- Yang, Xi,Yasukawa, Tomohiro,Yamashita, Yasuhiro,Kobayashi, Shū
-
p. 15800 - 15806
(2021/10/25)
-
- Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions
-
A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.
- Yang, Yu-Ming,Yan, Wei,Hu, Han-Wei,Luo, Yimin,Tang, Zhen-Yu,Luo, Zhuangzhu
-
p. 12344 - 12353
(2021/09/02)
-
- Bioinspired Radical-Mediated Transition-Metal-Free Synthesis of N-Heterocycles under Visible Light
-
A redox-active iminoquinone motif connected with π-delocalized pyrene core has been reported that can perform efficient two-electron oxidation of a class of substrates. The design of the molecule was inspired by the organic redox cofactor topaquinone (TPQ), which executes amine oxidation in the enzyme, copper amine oxidase. Easy oxidation of both primary and secondary alcohols happened in the presence of catalytic KOtBu, which could reduce the ligand backbone to its iminosemiquinonate form under photoinduced conditions. Moreover, this easy oxidation of alcohols under aerobic condition could be elegantly extended to multi-component, one-pot coupling for the synthesis of quinoline and pyrimidine. This organocatalytic approach is very mild (70 °C, 8 h) compared to a multitude of transition-metal catalysts that have been used to prepare these heterocycles. A detailed mechanistic study proves the intermediacy of the iminosemiquinonate-type radical and a critical hydrogen atom transfer step to be involved in the dehydrogenation reaction.
- K. Bains, Amreen,Ankit, Yadav,Adhikari, Debashis
-
p. 324 - 329
(2020/11/30)
-
- Electronic Asymmetry of an Annelated Pyridyl-Mesoionic Carbene Scaffold: Application in Pd(II)-Catalyzed Wacker-Type Oxidation of Olefins
-
The two donor modules of an annelated pyridyl-mesoionic carbene ligand (aPmic) have different σ- and π-bonding characteristics leading to its electronic asymmetry. A Pd(II) complex 1 featuring aPmic catalyzes the oxidation of a wide range of terminal olefins to the corresponding methyl ketones in good to excellent yields in acetonitrile. The catalytic reaction is proposed to proceed via syn-peroxypalladation and a subsequent rate-limiting 1,2-hydride shift, which is supported by kinetic studies. The electronic asymmetry of aPmic renders a well-defined coordination sphere at Pd. The favored arrangement of reactants on the metal center features an olefin trans to the pyridyl module and a tbutylperoxide trans to the carbene. This arrangement gains added stability by the π-delocalization paved by the compatible orbitals on Pd, the pyridyl module, and the olefin that is perpendicular to the Pd(aPmic) plane. The π-interactions are absent in an alternate arrangement wherein the olefin is trans to the carbene. Density functional theory studies reveal the matching orbital overlaps responsible for the preferred arrangement over the other. This work provides an orbital description for the electronic asymmetry of aPmic.
- Bera, Jitendra K.,Dutta, Indranil,Kunnikuruvan, Sooraj,Reshi, Noor U Din,Saha, Sayantani,Yadav, Suman
-
p. 11385 - 11393
(2020/11/23)
-
- Cobalt-Catalyzed Reductive C-O Bond Cleavage of Lignin β-O-4 Ketone Models via in Situ Generation of the Cobalt-Boryl Species
-
An efficient and mild method for reductive C-O bond cleavage of lignin β-O-4 ketone models was developed to afford the corresponding ketones and phenols with PDI-CoCl2 as the precatalyst and diboron reagent as the reductant. The synthetic utility of the methodology was demonstrated by depolymerization of a polymeric model and gram-scale transformation. Mechanistic studies suggested that this transformation involves steps of carbonyl insertion, 1,2-Brook type rearrangement, β-oxygen elimination, and rate-limiting regeneration of the catalytic active Co-B species.
- Gao, Kecheng,Xu, Man,Cai, Cheng,Ding, Yanghao,Chen, Jianhui,Liu, Bosheng,Xia, Yuanzhi
-
supporting information
p. 6055 - 6060
(2020/08/12)
-
- Palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters
-
Functional group transfer reactions are an important synthetic tool in modern organic synthesis. Herein, we developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides with thioethers and thioesters. The synthetic utility and practicality of this catalytic protocol are demonstrated in a wide range of successful transformations (>70 examples). This catalytic protocol is applicable in carbonylative coupling processes as well, and the first example of carbonylative methylthioesterification of aryl halides has been achieved. Notably, this work also provides an approach to using natural products, such as methionine and selenomethionine, as the functional group sources.
- Li, Yahui,Bao, Gao,Wu, Xiao-Feng
-
p. 2187 - 2192
(2020/03/11)
-
- Design, synthesis, and biological evaluation of novel dual PPARα/δ agonists for the treatment of T2DM
-
Dual PPARα/δ agonists have been considered as potential therapeutics for the treatment of type 2 diabetes mellitus. After comprehensive structure–activity relationship study based on GFT505, a novel dual PPARα/δ agonist compound 6 was identified with highly activities on PPARα/δ and higher selectivity against PPARγ than that of GFT505. The modeling study revealed that compound 6 binds well to the binding pockets of PPARα and PPARδ, which formed multiple hydrogen bonds with key residues related to the activation of PPARα and PPARδ. Moreover, oral glucose tolerance test exhibited that compound 6 exerts dose-dependent anti-diabetic effects in ob/ob mice and reveals similar potency to that of GFT505, the most advanced candidate in this field. These findings suggested that compound 6 is a promising candidate for further researches, and the extended chemical space might help us to explore better PPARα/δ agonist.
- Deng, Liming,Hu, Lijun,Li, Zheng,Ren, Qiang,Wang, Xuekun,Xie, Rongrong,Zhou, Zongtao
-
-
- B2cat2-Mediated Reduction of Sulfoxides to Sulfides
-
An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
- Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
-
supporting information
p. 3009 - 3012
(2020/03/25)
-
- Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2pressure
-
Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2. This journal is
- Fujita, Shu,Mitsudome, Takato,Mizugaki, Tomoo,Yamaguchi, Sho,Yamasaki, Jun,Yamazoe, Seiji
-
supporting information
p. 8827 - 8833
(2020/11/23)
-
- Design, synthesis, and biological evaluation of new pyrazino[1,2-a]benzimidazole derivatives as selective cyclooxygenase (COX-2) inhibitors
-
A new class of pyrazino[1,2-a]benzimidazole derivatives possessing the SO2Me pharmacophore at the para position of the C-3 phenyl ring was designed, synthesized, and tested for their cyclooxygenase-2 (COX-2) inhibitory, anti-cancer and anti-platelet aggregation activities. In vitro COX-1/COX-2 inhibition studies showed that 2-(4-methylphenyl)-1-methylene-3-(4-(methylsulfonyl)phenyl)-1,2-dihydropyrazino-[1,2-a]benzimidazole (5g) was the most potent COX-2 inhibitor (IC50 = 0.08 μM) and 2-(3,4,5-trimethoxyphenyl)-1-methylene-3-(4-(methylsulfonyl)phenyl)-1,2-dihydropyrazino-[1,2-a]benzimidazole (5m) had the highest selectivity index (SI > 909). Cytotoxicity of the synthesized compounds was also determined against the MCF-7 cell line. Most compounds were cytotoxic against MCF-7 cells and our results showed that compound 5m exhibited the highest anti-proliferative activity compared to the reference compound, cisplatin. Our data also indicated that compound 5k was the most potent platelet aggregation inhibitor according to aggregometry test results.
- Azami Movahed, Mahsa,Daraei, Bahram,Shahosseini, Soraya,Esfahanizadeh, Marjan,Zarghi, Afshin
-
-
- Transition-Metal-Free Aryl-Heteroatom Bond Formation via C-S Bond Cleavage
-
Aryl-heteroatom bonds (C-Het) are almost ubiquitously present in chemical molecules. However, methods for diverse C-Het bond formations from a simple substrate are limited. Herein, we report a convenient and efficient C-S bond transformation of aryl sulfoniums to various C-Het bonds (C-O, C-S, C-Sn, C-Si, C-Se) in the absence of any transition-metal catalyst. These reactions proceeded in mild conditions with a wide substrate scope.
- Zhao, Jian-Nan,Kayumov, Muzaffar,Wang, Dong-Yu,Zhang, Ao
-
supporting information
p. 7303 - 7306
(2019/10/02)
-
- A Deoximation Method for Deprotection of Ketones and Aldhydes Using a Graphene-Oxide-Based Co-catalysts System
-
The deoximation of a wide range of ketoximes and aldoximes to their corresponding carbonyl compounds with high yields has been achieved using graphene oxide (GO) and sodium nitrite (NaNO2) as highly efficient catalysts and air as the green oxidant under mild conditions. The mechanism of deprotection and recycling use of catalyst were revealed in deep experiment. The carboxylic acid groups on the GO were essential for high catalytic activity. (Figure presented.).
- Tong, Qiaolin,Liu, Yang,Gao, Xuezhi,Fan, Zhanfang,Liu, Tianfu,Li, Bo,Su, Dangsheng,Wang, Qinghe,Cheng, Maosheng
-
supporting information
p. 3137 - 3145
(2019/05/01)
-
- Nucleophilic Organic Base DABCO-Mediated Chemospecific Meinwald Rearrangement of Terminal Epoxides into Methyl Ketones
-
Nucleophilic organic base DABCO (1,4-diazabicyclo[2.2.2]octane)-mediated Meinwald rearrangement of various epoxides was investigated. 2-Aryl-, alkenyl-, and alkynylepoxides generate the corresponding methyl ketones chemospecifically in good to excellent yields. The current DABCO-mediated Meinwald rearrangement of epoxides features readily accessible starting materials, a wide substrate scope, a transition-metal- and acid-free environment, and chemospecificity in the isomerization of epoxides.
- Li, Siqi,Shi, Yi,Li, Pingfan,Xu, Jiaxi
-
p. 4443 - 4450
(2019/04/30)
-
- Visible light-promoted formation of C-B and C-S bonds under metal- A nd photocatalyst-free conditions
-
A green, efficient, photoinduced synthesis of arylboronic esters and aryl sulfides has been developed. Bench stable arylazo sulfones were used as radical precursors for a photocatalyst- A nd additive-free carbon-heteroatom bond formation under visible light. The protocols are applicable to a wide range of substrates, providing products in good yields.
- Blank, Lena,Fagnoni, Maurizio,Protti, Stefano,Rueping, Magnus
-
p. 1243 - 1252
(2019/02/26)
-
- A molybdenum based metallomicellar catalyst for controlled and chemoselective oxidation of activated alcohols in aqueous medium
-
A surfactant based oxodiperoxo molybdenum complex, which could activate molecular oxygen, has been employed as a catalyst for controlled oxidation of benzylic alcohols to corresponding carbonyls. The oxidation reactions were carried out under aqueous environment, however, in the absence of any extraneous base or co-catalyst. Sensitive/oxidizable functional groups like cyano, sulfide, hydroxyl, aryl-hydroxyl, alkene (internal/terminal), alkyne (internal/terminal), and acetal were tolerated during the transformations. Such selectivity is attributed to the mild nature of the catalyst. The methodology could also be scaled-up for multi-gram synthesis and the protocol is likely to find practical use since it requires an inexpensive recyclable-catalyst and easily available oxidant (under green conditions). A plausible mechanism is proposed with the help of preliminary computational study.
- Thiruvengetam, Prabaharan,Chakravarthy, Rajan Deepan,Chand, Dillip Kumar
-
p. 123 - 133
(2019/07/19)
-
- Preparation method of aromatic ketone
-
The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
- -
-
Paragraph 0056; 0057; 0058; 0060
(2018/09/11)
-
- C-S cross-coupling reactions catalyzed by a non-symmetric phosphinito-thiophosphinito PSCOP-Ni(II) pincer complex
-
A new non-symmetric phosphinito-thiophosphinito POCSP-Ni(II) pincer compound was synthetized and characterized. The molecular structure of [NiCl{C6H3-2-(OPPh2)-6-(SPPh2)}] (1) was unequivocally determined by single crystal X-ray diffraction analysis, showing the Ni center to be located into a slightly distorted square planar geometry. This compound was used as efficient catalyst in C-S couplings of disulfides with iodobenzenes, exhibiting good activity and selectivity as well as tolerance to different functional groups.
- Serrano-Becerra, Juan M.,Valdés, Hugo,Canseco-González, Daniel,Gómez-Benítez, Valente,Hernández-Ortega, Simón,Morales-Morales, David
-
p. 3377 - 3380
(2018/08/06)
-
- A visible-light photocatalytic thiolation of aryl, heteroaryl and vinyl iodides
-
The general catalytic synthesis of aryl and vinyl thioethers from readily available halides remains a challenge. Herein we report a unified method for the thiolation of aryl and vinyl iodides with dialkyl disulfides using visible light photoredox catalysis. A range of thioether products bearing diverse functional groups can be accessed in high yield and with excellent chemoselectivity. We demonstrate the versatility of this method through the expedient synthesis of a family of thioether-rich natural products. A detailed investigation of the photocatalytic mechanism is presented from both steady-state and time-resolved luminescent quenching as well as transient absorption spectroscopy experiments.
- Czyz,Weragoda,Monaghan,Connell,Brzozowski,Scully,Burton,Lupton,Polyzos
-
supporting information
p. 1543 - 1551
(2018/03/08)
-
- Pd-catalyzed Oxidative Cross-coupling of Alkyl Chromium(0) Fischer Carbene Complexes with Organoboronic Acids
-
Alkyl chromium(0) carbene complexes have been explored as the cross-coupling partners in the palladium-catalyzed reaction with aryl or alkenyl boronic acids. This coupling reaction displays the versatile reactivities of alkyl chromium(0) carbenes under palladium catalysis. Mechanistically, this transformation is proposed to involve deprotonation of the alkyl chromium carbene substrate to generate a vinyl chromium anion intermediate that undergoes transmetalation to organopalladium species and reductive elimination.
- Wang, Kang,Yang, Jinghui,Yao, Xingqi,Wang, Jianbo
-
supporting information
p. 3165 - 3168
(2018/10/15)
-
- Cesium carbonate-promoted synthesis of aryl methyl sulfides using: S -methylisothiourea sulfate under transition-metal-free conditions
-
In the presence of cesium carbonate, an efficient synthesis of aryl methyl sulfides by the reactions of aryl halides with commercially available S-methylisothiourea sulfate is developed. This odourless and highly crystalline solid can be used as the subst
- Zhang, Caiyang,Zhou, You,Huang, Jintao,Tu, Canhui,Zhou, Xiaoai,Yin, Guodong
-
p. 6316 - 6321
(2018/09/10)
-
- Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
-
A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
- Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
-
p. 3275 - 3284
(2018/03/25)
-
- Palladium-Catalyzed Thiomethylation via a Three-Component Cross-Coupling Strategy
-
In this report, the combination of masked inorganic sulfur and dimethyl carbonate was designed to achieve thiomethylated cross coupling of aryl chlorides. Remarkably, this powerful strategy realized thiomethylation of nucleosides bearing unprotected ribose, chloride-containing pharmaceuticals with late-stage coupling, and herbicides possessing multiple heteroatoms and steric hindrance. Moreover, this protocol is practically amenable to multigram-scale synthesis with a lower catalysis loading and a higher yield.
- Wang, Ming,Qiao, Zongjun,Zhao, Jiaoyan,Jiang, Xuefeng
-
supporting information
p. 6193 - 6197
(2018/09/25)
-
- Iodine-Promoted Semmler–Wolff Reactions: Step-Economic Access to meta-Substituted Primary Anilines via Aromatization
-
An atom- and step-economic access to an array of unprotected meta-substituted primary anilines was disclosed using the Semmler–Wolff reaction, promoted by molecular iodine. Therein, noble metal catalysts and inert atmosphere are unnecessary while the forcing reaction conditions and the lengthy synthesis can be avoided. The synthetic utility of this approach is evident in the de novo syntheses of three bioactive molecules with good total yields.
- Wang, Shi-Ke,You, Xia,Zhao, Da-Yuan,Mou, Neng-Jie,Luo, Qun-Li
-
supporting information
p. 11757 - 11760
(2017/09/07)
-
- Methyl aryl thioether compound, and synthetic method and applications thereof
-
The invention discloses a methyl aryl thioether compound represented by formula 2, and a synthetic method and applications thereof. According to the synthetic method, in a reaction solvent, an aryl halide or an aromatic halide, dimethyl carbonate, and potassium thioacetate are taken as reaction raw materials, reaction is carried out in the presence of metal palladium catalyst under the action of a ligand and an alkali so as to obtain the methyl aryl thioether compound. The reaction conditions of the synthetic method are mild; the raw materials are cheap and easily available; reaction operation is simple; yield is relatively high. The methyl aryl thioether compound can be used for providing skeleton structures for the synthesis of a plurality of natural products and medicines, and can be widely applied in industrialized large-scale production.
- -
-
Paragraph 0071; 0072; 0073
(2017/07/21)
-
- Acceptorless dehydrogenation and dehydrogenative coupling of alcohols catalysed by protic NHC ruthenium complexes
-
A new family of protic NHC Ru complexes ligated with a phosphine-tethered imidazole moiety were prepared, which can act as excellent catalysts for acceptorless dehydrogenation of secondary alcohols and dehydrogenative coupling of primary and secondary alcohols, thus leading to the formation of a variety of carbonyl compounds with release of H2.
- Chang, Weihong,Gong, Xue,Wang, Shuizhong,Xiao, Ling-Ping,Song, Guoyong
-
supporting information
p. 3466 - 3471
(2017/04/26)
-
- Synthesis and biological evaluation of new imidazo[1,2-a]pyridine derivatives as selective COX-2 inhibitors
-
The close structural similarity between cyclooxygenase (COX) isoforms and also the lack of potent selective COX-2 inhibitors with low side effects, stimulate the development of new highly selective COX-2 inhibitors. In this study, a group of imidazo[1,2-a]pyridines was designed, synthesized and investigated to identify potent and selective COX-2 inhibitors. In vitro COX inhibition assay showed that all derivatives were selective COX2 inhibitors with IC50 values in the highly potent 0.07-0.18 μM range and COX-2 selectivity indexes (SI) in 57-217 range. 2-(4-(methylsulfonyl)phenyl)-3-(morpholinomethyl)H-imidazo[1,2-a]pyri-dine (6f) which possessing p-methylsulfonyl phenyl at C-2 of imidazo[1,2-a]pyridine ring, exhibited the highest COX-2 inhibitory selectivity and potency. Molecular modeling and docking studies indicated that synthesized compounds have a binding similar to that of the known inhibitor SC-558 and also methylsulfonyl group can be inserted into the secondary pocket of COX-2. The ability of synthesized compounds for inhibition of platelet aggregation was also determined. Our results demonstrated that 6f was the most potent platelet aggregation inhibitor as well.
- Movahed, Mahsa Azami,Daraei, Bahram,Zarghi, Afshin
-
p. 793 - 799
(2016/09/28)
-
- Mild Ti-mediated transformation of t-butyl thio-ethers into thio-acetates
-
We report a straightforward method for the rapid conversion of thio-ethers to thio-acetates using TiCl4, in good to excellent yields. The reaction conditions tolerate a variety of functional groups, including halide, nitro, ether, thiophene and acetylene functionalities. A catalytic variant of this reaction is also described. This journal is
- Pijper, Thomas C.,Robertus, Jort,Browne, Wesley R.,Feringa, Ben L.
-
supporting information
p. 265 - 268
(2015/01/16)
-
- Azo compound, aqueous solution, ink composition, ink for inkjet recording, inkjet recording method, ink cartridge for inkjet recording, and inkjet recorded material
-
There is provided a compound represented by the following formula (1): wherein each of R1a to R1k independently represents a hydrogen atom or a monovalent substituent, the substituents may combine with each other to form a ring, each of M1a and M1b independently represents a hydrogen atom or a monovalent counter cation, Y1 represents a nitrogen atom or a carbon atom having a hydrogen atom or monovalent substituent, A1 represents an aromatic group, and the aromatic group represented by A1 may contain a heteroatom or may have a substituent.
- -
-
Paragraph 0403; 0404
(2014/05/06)
-
- Hydrogenation of sulfoxides to sulfides under mild conditions using ruthenium nanoparticle catalysts
-
The first demonstration of the hydrogenation of sulfoxides under atmospheric H2 pressure is reported. The highly efficient reaction is facilitated by a heterogeneous Ru nanoparticle catalyst. The mild reaction conditions enable the selective hydrogenation of a wide range of functionalized sulfoxides to the corresponding sulfides. The high redox ability of RuO x nanoparticles plays a key role in the hydrogenation.
- Mitsudome, Takato,Takahashi, Yusuke,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
-
supporting information
p. 8348 - 8351
(2014/08/18)
-
- Highly efficient deoxygenation of sulfoxides using hydroxyapatite-supported ruthenium nanoparticles
-
We report the first example of the deoxygenation of sulfoxides using heterogeneous catalysts with alcohols as environmentally friendly reducing reagents. Hydroxyapatitesupported Ru nanoparticles (RuNPs/HAP) act as a highly efficient and reusable heterogeneous catalyst for deoxygenation of sulfoxides using alcohols as reductants. The catalytic activity of Ru nanoparticles is outstanding compared to other metal nanoparticles such as Pt, Pd, Rh, and Au nanoparticles. RuNPs/HAP can also catalyze the selective deoxygenation of various sulfoxides, giving the corresponding sulfides in excellent yields.
- Takahashi, Yusuke,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
-
supporting information
p. 420 - 422
(2014/04/17)
-
- Efficient and recyclable rare earth-based catalysts for Friedel-Crafts acylations under microwave heating: Dendrimers show the way
-
The catalytic system involving Sc(OTf)3 and a dendritic terpyridine ligand is able to promote the Friedel-Crafts acylation of a wide range of aromatics under microwave irradiation. The expected products are obtained in high yields after short reaction times and the nano-sized catalyst can be recovered and successfully used in 12 consecutive runs.
- Perrier, Arnaud,Keller, Michel,Caminade, Anne-Marie,Majoral, Jean-Pierre,Ouali, Armelle
-
supporting information
p. 2075 - 2080
(2013/09/24)
-
- Stereoselective synthesis and anti-proliferative effects on prostate cancer evaluation of 5-substituted-3,4-diphenylfuran-2-ones
-
Series of 5-substituted-3,4-diphenylfuran-2-ones were stereoselectively prepared. Their potential anti-proliferative effects on prostate cancer and some of their cyclooxygenases (COXs) inhibitory activities were evaluated. Structure-activity relationship (SAR) data, acquired by substituent modification at the para-position and ortho-position of the C-3 phenyl ring and 5-substituted modification of the central furanone, showed that 3-(2-chloro-phenyl)-4-(4-methanesulfonyl-phenyl)-5-(1-methoxy-ethyl) -5H-furan-2-one (13p) was the most potent compound and could effectively reduce the proliferation of prostate cancer cells (PC3 cell IC50 = 20 μM; PC3 PCDNA cell IC50 = 5 μM; PC3 SKP2 cell IC50 = 5 μM; DU145 cell IC50 = 25 μM). The cell cycle analysis for 13p in DU145 indicated that 13p may induce G1 phase arrest.
- Liu, Gai-Zhi,Xu, Hai-Wei,Wang, Peng,Lin, Zong-Tao,Duan, Ying-Chao,Zheng, Jia-Xin,Liu, Hong-Min
-
p. 323 - 336
(2013/10/01)
-
- Copper(I) iodide-catalysed aerobic oxidative synthesis of imidazo [1,2-α]pyridines from 2-aminopyridines and methyl ketones
-
We report here an operationally simple copper-catalysed synthesis of imidazo [1,2-α]pyridines through C-H activation with oxidative linkage of two C-N bonds under very mild conditions using molecular oxygen as a sole oxidant. The process allows the quick assembly of imidazo [1,2-α]pyridines including the antiulcer drug zolimidine from inexpensive and readily available 2-aminopyridines and methyl ketones with broad range of functional group tolerance.
- Mohan, Darapaneni Chandra,Donthiri, Ramachandra Reddy,Rao, Sadu Nageswara,Adimurthy, Subbarayappa
-
supporting information
p. 2217 - 2221
(2013/10/01)
-
- Deoxygenation of sulfoxides to sulfides with thionyl chloride and triphenylphosphine: Competition with the Pummerer reaction
-
Although a number of methods have been developed to reduce sulfoxides to sulfides, many of these processes are limited by side reactions, low yields, poorly available reagents, or harsh reaction conditions. We recently studied the reaction of various sulfoxides with SOCl2 and Ph3P. We were able to obtain the corresponding sulfides in excellent yields (>90%) when aliphatic and aromatic sulfoxides were treated with SOCl2 as a catalyst and Ph3P in THF at room temperature.
- Jang, Yujin,Kim, Kyoung Tae,Jeon, Heung Bae
-
p. 6328 - 6331
(2013/07/25)
-
- Friedel-Crafts acylation using bismuth triflate in [BMI][PF6]
-
Bismuth trifluoromethanesulfonate was found to be a good catalyst for the Friedel-Crafts acylation. Bismuth triflate immobilized in an ionic liquid was the most efficient catalytic system. Bismuth triflate in [BMI][PF6] catalyzes this reaction under microwave irradiation allowing the rapid synthesis of aryl ketones in excellent yields. The catalyst system was easily recovered and reused several times.
- Tran, Phuong Hoang,Duus, Fritz,Le, Thach Ngoc
-
experimental part
p. 222 - 224
(2012/01/30)
-
- Friedel-crafts acylation reactions using esters
-
Intermolecular and intramolecular Friedel-Crafts acylation reactions of various aliphatic and aromatic esters at room temperature with the use of very simple reagents and activating groups in are described. The products were obtained in good yield (60-85 %). The detailed mechanistic pathway was studied by DFT calculations and supported by experimental evidence. Copyright
- Chavan, Subhash P.,Garai, Sumanta,Dutta, Achintya Kumar,Pal, Sourav
-
supporting information
p. 6841 - 6845
(2013/02/22)
-
- Highly atom-economic, catalyst- and solvent-free oxidation of sulfides into sulfones using 30% aqueous H2O2
-
Highly atom-efficient oxidation of sulfides into sulfones under solvent- and catalyst-free reaction conditions using a 30% aqueous solution of H 2O2 at 75 °C is reported. A structurally diverse set of phenyl alkyl-, phenyl benzyl-, benzyl alkyl-, dialkyl-, heteroaryl alkyl- and cyclic sulfides were transformed into sulfones regardless of the aggregate state and electronic nature of the substituents. In spite of the heterogeneous reaction mixtures throughout the work, no difficulties with stirring and reaction progress were noted. In numerous cases, only 10 mol% excess of H 2O2 was used, thus contributing considerably to the high atom economy of the process. Some solid substrates required a variable excess of hydrogen peroxide; however, the reactions were performed strictly without organic solvents. The transformation was demonstrated to be amenable for scale-up with both liquid and solid sulfides. In addition, isolation and purification of the crude products can be simply done with only filtration and crystallization.
- Jereb, Marjan
-
supporting information
p. 3047 - 3052,6
(2020/09/16)
-
- Aryl methyl sulfides as substrates for rhodium-catalyzed alkyne carbothiolation: Arene functionalization with activating group recycling
-
A Rh(I)-catalyzed method for the efficient functionalization of arenes is reported. Aryl methyl sulfides are combined with terminal alkynes to deliver products of carbothiolation. The overall process results in reincorporation of the original arene functional group, a methyl sulfide, into the products as an alkenyl sulfide. The carbothiolation process can be combined with an initial Rh(I)-catalyzed alkene or alkyne hydroacylation reaction in three-component cascade sequences. The utility of the alkenyl sulfide products is also demonstrated in simple carbo- and heterocycle-forming processes. We also provide mechanistic evidence for the course of this new process.
- Hooper, Joel F.,Chaplin, Adrian B.,Gonzalez-Rodriguez, Carlos,Thompson, Amber L.,Weller, Andrew S.,Willis, Michael C.
-
supporting information; experimental part
p. 2906 - 2909
(2012/03/27)
-
- Design, synthesis and biological evaluation of novel 4-hydroxybenzene acrylic acid derivatives
-
A series of 4-hydroxybenzene acrylic acid derivatives were designed and synthesized based on the ferulic acid of natural active ingredients. The tested compound 5a, 5f and 6a have significant anti-inflammatory activity with suppression rates of 45.29%, 44.75% and 24.11%, respectively, compared with that of indomethacin, and their cardiac toxicity was not observed. The structure-function relationship shows that the p-hydroxyl group on the α-position benzene ring, particularly if acetylated, contributes to the considerable anti-inflammatory activity; that the carboxyl group on the double bond, if esterified, also contributes to the anti-inflammatory activity; that the p-methylsulfonyl group on the other benzene ring, whose introduction is due to the COX-2 selectivity, also contributes to anti-inflammatory activity surprisingly.
- Mao, Jin-Long,Ran, Xiang-Kai,Tian, Jing-Zhen,Jiao, Bo,Zhou, Hong-Lei,Chen, Li,Wang, Zhen-Guo
-
scheme or table
p. 1549 - 1553
(2011/04/22)
-
- Bioactive sulfoximines: Syntheses and properties of Vioxx analogs
-
The syntheses and biological profiles of sulfoximine-based Vioxx analogs 2 are described. Interesting data have been obtained for 2a, which shows a selective COX-2 inhibition (albeit not as strong as Vioxx itself) exhibiting reduced hERG activity compare to the parent sulfone Vioxx (1).
- Park, Seong Jun,Buschmann, Helmut,Bolm, Carsten
-
scheme or table
p. 4888 - 4890
(2011/09/21)
-
- (N-Heterocyclic Carbene)-Pd-catalyzed anaerobic oxidation of secondary alcohols and domino oxidation-arylation reactions
-
The use of commercially available (SIPr)Pd(cinnamyl)Cl (SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene) as a precatalyst for the anaerobic oxidation of secondary alcohols is described. The use of this complex allows for a drastic reduction in the reaction times and catalyst loading when compared to the unsaturated counterpart. This catalytic system is compatible with the use of microwave dielectric heating, decreasing even further catalyst loading and reaction times. Domino Pd-catalyzed oxidation-arylation reactions of secondary alcohols are also presented.(Figure Presented)
- Landers, Brant,Berini, Christophe,Wang, Chao,Navarro, Oscar
-
experimental part
p. 1390 - 1397
(2011/05/02)
-
- Highly efficient gold nanoparticle catalyzed deoxygenation of amides, sulfoxides, and pyridine N-oxides
-
Selective deoxygenation is one of the most important reactions in the areas of total synthesis, biological chemistry, and transformation of renewable biomass resources.To date, many useful methods for the selective deoxygenation of oxygen-containing organic molecules, such as amides, nitro compounds, epoxides, sulfoxides, and those with Noxide groups, have been developed. However, these methods often include stoichiometric reactions. Some successful catalysts have been reported,but most of them are homogeneous systems and still suffer from low activities and selectivities, harsh reaction conditions, and tedious workup procedures. Therefore, further development of highly efficient heterogeneous catalysts for selective deoxygenations is highly desired.
- Mikami, Yusuke,Noujima, Akifumi,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
-
experimental part
p. 1768 - 1772
(2011/03/21)
-
- Efficient synthesis of aryl methyl sulfide derivatives using (methylthio)trimethylsilane as methylthiolation reagent
-
The synthesis of various aryl methyl sulfides has been achieved by treatment of nitroarenes with a combination of (methylthio)trimethylsilane and cesium carbonate in dimethylsulfoxide. This reaction gives access to aryl methyl sulfide derivatives in high yields. Copyright
- Qiao, Qi,Dominique, Romyr,Sidduri, Achyutharao,Lou, Jianping,Goodnow, Robert A.
-
scheme or table
p. 3691 - 3698
(2010/12/25)
-
- Diaryl-dithiolanes and -isothiazoles: COX-1/COX-2 and 5-LOX-inhibitory, {radical dot}OH scavenging and anti-adhesive activities
-
Three series of non-steroidal anti-inflammatory drugs (NSAIDs) inhibiting the cyclooxygenase/5-lipoxygenase (COX/5-LOX) pathways as such as formation of hydroxyl radicals and adhesion were prepared: 4,5-diaryl isothiazoles, 4,5-diaryl 3H-1,2-dithiole-3-thiones and 4,5-diaryl 3H-1,2-dithiole-3-ones. The aim of the present study was to develop substances which can intervene into the inflammatory processes via different mechanisms of action as multiple target non-steroidal anti-inflammatory drugs (MTNSAIDs) with increased anti-inflammatory potential. The current lead 11a was evaluated in COX-1/2, 5-LOX and {radical dot}OH scavenging in vitro assays and in a static adhesion assay where it proved to inhibit adhesion. Moreover, 11a treatment attenuated expression of macrophage adhesion molecule-1 (Mac-1) on extravasated polymorphonuclear leukocytes (PMNs) which indicates that the activation was reduced. The assays used are predictive for the in vivo efficacy of test compounds as shown for 11a in a peritonitis model of acute inflammation in mice. Thus, the novel 5-LOX/COX and {radical dot}OH inhibitor 11a possesses anti-inflammatory activity that, in addition to COX/5-LOX inhibition, implicates effects on leukocyte-endothelial interactions.
- Scholz, Michael,Ulbrich, Holger K.,Soehnlein, Oliver,Lindbom, Lennart,Mattern, Andreas,Dannhardt, Gerd
-
supporting information; experimental part
p. 558 - 568
(2009/08/07)
-
- Synthesis of some new pyrazolines and isoxazoles carrying 4-methylthiophenyl moiety as potential analgesic and antiinflammatory agents
-
A series of new pyrazolines 3a-m and isoxazoies 4a-k have been synthesized from 4-acetylthioanisole, 1 with aryl aldehydes through α, β-unsaturated ketones. The structures of the newly synthesized compounds have been confirmed on the basis of elemental analysis and spectral studies. The newly synthesized title compounds have been tested for their analgesic and antiinflammatory activity. Some of the compounds exhibited encouraging results.
- Karabasanagouda,Adhikari, Airody Vasudeva,Girisha
-
experimental part
p. 430 - 437
(2009/12/26)
-
- Oxygen and base-free oxidative heck reactions of arylboronic acids with olefins
-
A mild and efficient protocol for palladium-catalyzed oxidative Heck reactions of arylboronic acids with both electron-rich and -deficient olefins is described. In contrast to the normal oxidative Heck coupling, this new method works in the absence of a base, oxygen, or other external oxidants. With a wide variety of substrates tolerated, the method broadens the scope of palladium-catalyzed coupling reactions. Copyright
- Ruan, Jiwu,Li, Xinming,Saidi, Ourida,Xiao, Jianliang
-
p. 2424 - 2425
(2008/09/18)
-
- Lanthanide triflate-catalyzed arene acylation. Relation to classical Friedel-Crafts acylation
-
(Chemical Equation Presented) Lanthanide trifluoromethanesulfonates, Ln(OTf)3 (OTf- = trifluoromethanesulfonate), serve as effective precatalysts for the rapid, regioselective, intermolecular acylation of activated arenes. This contribution probes mechanism and metal ionic radius effects in the catalytic lanthanide triflate-mediated acylation of anisole with acetic anhydride. Kinetic studies of Ln(OTf)3 (Ln = La, Eu, Yb, Lu)-mediated anisole acylation with acetic anhydride in nitromethane reveal the rate law ν ~ k3 [Ln3+]1[acetic anhydride]1[anisole]1. Eyring and Arrhenius analyses yield ΔH? = 12.9 (4) kcal·mol-1, ΔS? = -44.8 (1.3) e.u., and Ea = 13.1 (4) kcal·mol-1 for Ln = Yb, with the negative ΔS? implying a highly organized transition state. The observed primary kinetic isotope effect of k H/kD = 2.6 ± 0.15 is consistent with arene C-H bond scission in the turnover-limiting step. The proposed catalytic pathway involves precatalyst formation via interaction of Ln(OTf)3 with acetic anhydride, followed by Ln3+-anisole π-complexation, substrate-electrophile σ-complex formation, and turnover-limiting C-H bond scission. Lanthanide size effects on turnover frequencies are consistent with a transition state lacking significant ionic radius-dependent steric constraints. Substrate-Ln3+ interactions using paramagnetic Gd3+ and Yb3+ NMR probes and factors affecting reaction rates such as arene substituent and added LiClO4 cocatalyst are also explored.
- Dzudza, Alma,Marks, Tobin J.
-
p. 4004 - 4016
(2008/09/21)
-
- Competition between α-cleavage and energy transfer in α-azidoacetophenones
-
(Chemical Equation Presented) Molecular modeling demonstrates that the first excited state of the triplet ketone (T1K) in azide 1b has a (π,π*) configuration with an energy that is 66 kcal/mol above its ground state and its second excited state (T2K) is 10 kcal/mol higher in energy and has a (n,π*) configuration. In comparison, T 1K and T2K of azide 1a are almost degenerate at 74 and 77 kcal/mol above the ground state with a (n,π*) and (π,π*) configuration, respectively. Laser flash photolysis (308 nm) of azide 1b in methanol yields a transient absorption (λmax = 450 nm) due to formation of T1K, which decays with a rate of 2.1 × 10 -5 s-1 to form triplet alkylnitrene 2b (λmax = 320 nm). The lifetime of nitrene 2b was measured to be 16 ms. In contrast, laser flash photolysis (308 nm) of azide 1a produced transient absorption spectra due to formation of nitrene 2a (λ max = 320 nm) and benzoyl radical 3a (λmax = 370 nm). The decay of 3a is 2 × 10-5 s-1 in methanol, whereas nitrene 2a decays with a rate of ~91 s-1. Thus, T 1K (π,π*) in azide 1b leads to energy transfer to form nitrene 2b; however, α-cleavage is not observed since the energy of T 2K (n,π*) is 10 kcal/mol higher in energy than T 1K, and therefore, T2K is not populated. In azide 1a both α-cleavage and energy transfer are observed from T1K (n,π*) and T2K (π,π*), respectively, since these triplet states are almost degenerate. Photolysis of azide 1a yields mainly product 4, which must arise from recombination of benzoyl radicals 3a with nitrenes 2a. However, products studies for azide 1b also yield 4b as the major product, even though laser flash photolysis of azide 1b does not indicate formation of benzoyl radical 3b. Thus, we hypothesize that benzoyl radicals 3 can also be formed from nitrenes 2. More specifically, nitrene 2 does undergo α-photocleavage to form benzoyl radicals and iminyl radicals. The secondary photolysis of nitrenes 2 is further supported with molecular modeling and product studies.
- Muthukrishnan, Sivaramakrishnan,Mandel, Sarah M.,Hackett, John C.,Singh, Pradeep N. D.,Hadad, Christopher M.,Krause, Jeanette A.,Gudmundsdottir, Anna D.
-
p. 2757 - 2768
(2008/02/02)
-
- Alkyl- and arylthiolation of aryl halides catalyzed by fluorinated bis-imino-nickel NNN pincer complexes [NiCl2{C5H 3N-2,6-(CHNArf)2}]
-
The synthesis of bis-imino nickel(II) NNN pincer complexes of the type [NiCl2{C5H3N-2,6-(CHNArf) 2}]; Arf= C6H3-2,3-F2 (1), C6H3-2,5-F2 (2), C6H 3-3,4-F2 (3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 (5), C6H 2-2,3,6-F3 (6), C6H2-2,4,5-F 3 (7), C6H2-2,4,6-F3 (8), has been achieved and their reactivity in alkyl- and arylthiolation reactions of halobenzenes examined. The use of fluorinated substituents Arf on the imines has allowed the tuning of the electronics in these complexes and the influence of these substituents and those of the disulfides in the thiolation reactions have been analyzed.
- Baldovino-Pantaleon, Oscar,Hernandez-Ortega, Simon,Morales-Morales, David
-
p. 236 - 242
(2007/10/03)
-