- Halogen-Bond-Promoted Photoactivation of Perfluoroalkyl Iodides: A Photochemical Protocol for Perfluoroalkylation Reactions
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A new protocol for photochemical perfluoroalkylation reactions using perfluoroalkyl iodide, amine additive, and THF solvent is reported. This protocol does not require a photoredox catalyst and proceeds at ambient temperature with irradiation from a compact fluorescent lamp, low-intensity UV lamp, or sunlight. This protocol can be applied to the synthesis of perfluoroalkyl-substituted phenanthridines as well as effect the iodo-perfluoroalkylation of alkenes/alkynes and the C-H perfluoroalkylation of electron-rich arenes and heteroarenes. This C-H perfluoroalkylation reaction offers a unique method for site-selective labeling of oligopeptides at the tryptophan residue.
- Wang, Yaxin,Wang, Junhua,Li, Guo-Xing,He, Gang,Chen, Gong
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- Preparation of unsymmetrical biaryls via Ni- or Pd-catalyzed coupling of aryl chlorides with arylzincs
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Unsymmetrical biaryls may be prepared in an efficient manner using aryl chlorides as substrates in Negishi-type cross-coupling reactions with arylzinc reagents via either Ni- or Pd-catalysis. Since a wide range of functional groups (e.g., nitrile, carbonyl, ester) tolerate arylzinc compounds, this methodology allows for the direct synthesis of biaryls from aryl chlorides possessing these moieties.
- Miller, Joseph A.,Farrell, Robert P.
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- An efficient and cost-effective synthesis of 2-phenyl-3-aminopyridine
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The synthesis of 2-phenyl-3-aminopyridine, a key intermediate in the preparation of 2-phenyl-3-aminopiperidine, from 2-chloro-3-aminopyridine is described using an imine as a protecting group for an aminopyridine. The in situ protection of 2-chloro-3-amin
- Caron, Stephane,Massett, Steve S.,Bogle, David E.,Castaldi, Michael J.,Braish, Tamim F.
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- Asymmetric hydrogenation of 2-aryl-3-phthalimidopyridinium salts: Synthesis of piperidine derivatives with two contiguous stereocenters
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Asymmetric hydrogenation of 2-aryl-3-phthalimido-pyridinium salts catalyzed by the Ir/SegPhos catalytic system was described, leading to the corresponding chiral piperidine derivatives bearing two contiguous chiral centers, with high levels of enantioselectivities and diastereoselectivities. A gram-scale experiment has demonstrated the utility of this approach. The phthaloyl group could be easily removed and then smoothly converted to key intermediate (+)-CP-99994 as one of the neurokinin 1 receptor antagonists.
- Zhang, Xumu,Chen, Gen-Qiang,Zheng, Long-Sheng,Wang, Fangyuan,Ye, Xiang-Yu
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- A palladium complex confined in a thiadiazole-functionalized porous conjugated polymer for the Suzuki-Miyaura coupling reaction
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Porous organic polymers (POPs) with well-distributed and tunable functional groups acting as ligands for specific reactions are promising supports for confining useful novel metals such as Pd, Au, and Pd. Herein, a thiadiazole-containing POP has been successfully synthesized and used for immobilizing Pd species. Pd immobilized inside the micropores (2.3 nm) of the POP material is easily prepared owing to a large amount of the strong anchoring group, thiadiazole, which is intrinsically distributed in the as-prepared POP. The rigid thiadiazole-containing polymer can stabilize the central metal rather than poisoning it. The as-prepared catalyst shows excellent catalytic activity in Suzuki-Miyaura coupling reactions under mild reaction conditions and low catalyst loading. Importantly, the intrinsically distributed thiadiazole ligands can stabilize the Pd moiety, preventing aggregation and leaching, and afford excellent catalytic lifetimes. Consequently, the catalyst can be reused 10 times without a significant loss of its catalytic activity.
- Qian, Yingjie,Jeong, Sang Yung,Baeck, Sung-Hyeon,Jin, Myung-Jong,Shim, Sang Eun
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- Direct synthesis of hetero-biaryl compounds containing an unprotected NH2 group via Suzuki-Miyaura reaction
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Hetero-biaryl compounds were prepared via the Suzuki-Miyaura coupling reaction of hetero-aryl moieties containing an unprotected NH2 group and arylboronic acids. D-t-BPF was found to be an efficient ligand for the cross-coupling of NH2/su
- Itoh, Takahiro,Mase, Toshiaki
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- Discovery of novel 2-aryl-3-sulfonamido-pyridines (HoAns) as microtubule polymerization inhibitors with potent antitumor activities
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Microtubules play a vital role in cell mitosis. Drugs targeting taxol or vinca binding site of tubulin have been proved an effective way to against cancer. However, drug resistance and cancer recurrence are inevitable, there is an urgent need to search for new microtubule-targeting agents (MTAs). In our study, a series of novel 2-aryl-3-sulfonamido-pyridines (HoAns) had been designed, synthesized, and evaluated for their antiproliferative activities in vitro and in vivo. Among them, compound HoAn32 exhibited the most potent activity with IC50 values ranging from 0.170 to 1.193 μM in a panel of cancer cell lines. Mechanism studies indicated that compound HoAn32 bound to the colchicine site of β-tubulin, resulting in colony formation inhibition, G2/M phase cell cycle arrest, cell apoptosis as well as increased the generation of ROS in both RKO and SW620 cells. In addition, compound HoAn32 showed potent anti-vascular activity in vitro. Furthermore, compound HoAn32 also exhibited outstanding antitumor activity in SW620 xenograft tumor models without observable toxic effects, which was more potent than that of ABT-751. In conclusion, our findings suggest that compound HoAn32 may be a promising microtubule destabilizing agent and deserves for further development in cancer therapy.
- Zhu, Heping,Ying, Shilong,Zhou, Bingluo,Liang, Xiao,He, Quan,Song, Ping,Hu, Xinyang,Shi, Keqiang,Xiong, Mingteng,Jin, Hongchuan,Pan, Yuanjiang
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- Pyridine-2-aryl-3-sulfonamide compound as well as synthesis method and application thereof
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The invention discloses a pyridine-2-aryl-3-sulfonamide compound as well as a synthesis method and application thereof in preparation of an antitumor drug or tubulin polymerization inhibitor. The pyridine-2-aryl-3-sulfonamide compound has a structural general formula (I), X, Y and Z are selected from C or N atoms, and R1 represents a monosubstituted or polysubstituted group; r2 represents a monosubstituted or polysubstituted group; and R3 represents hydrogen or a different C1-5 alkoxy-substituted benzenesulfonyl group. The invention discloses application of pyridine-2-aryl-3-sulfonamide compounds in preparation of medicines. The pyridine-2-aryl-3-sulfonamide compounds are used as active ingredients for preparing antitumor medicines or tubulin polymerization inhibitors. The antitumor drugsare drugs for resisting colon cancer, breast cancer, liver cancer, lung cancer, stomach cancer or pancreatic cancer.
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Paragraph 0036; 0037; 0122; 0123
(2020/07/13)
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- METHODS FOR EXTERNAL BASE-FREE SUZUKI COUPLINGS
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The present disclosure describes a method of coupling a first aromatic compound to a second aromatic compound, the method comprising: (a) preparing a reaction mixture comprising the first aromatic compound, the second aromatic compound, a catalyst and water; the reaction mixture does not contain an external base, the reaction mixture having an initial pH of from 11 to 1; the catalyst having at least one group 10 atom; the first aromatic compound having a halogen, triflate or sulfonate substituent; the second aromatic compound having a boron-containing substituent; wherein, at least one of the first aromatic compound or the second aromatic compound includes one or more heteroatom; and (b) reacting the first aromatic compound and the second aromatic compound in the reaction mixture, the reaction mixture having a final pH following reaction of the first aromatic compound and the second aromatic compound.
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Paragraph 0035-0036
(2017/07/14)
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- Pd-Catalyzed Suzuki coupling reactions of aryl halides containing basic nitrogen centers with arylboronic acids in water in the absence of added base
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The Pd-catalyzed Suzuki coupling reactions of a series of aryl chlorides and aryl bromides containing basic nitrogen centers with arylboronic acids in water in the absence of added base are reported. The reactions proceed either partially or entirely under acidic conditions. After surveying twenty-two phosphorus ligands, high yields of products were obtained with aryl chlorides only when a bulky ligand, 2-(di-tert-butyl-phosphino)-1-phenyl-1H-pyrrole (cataCXiumPtB) was used. In contrast, aryl bromides produced high yields of products in the absence of both added base and added ligand. In order to explore the Suzuki coupling process entirely under acidic conditions, a series of reactions were conducted in buffered acidic media using several model substrates. 4-Chlorobenzylamine, in the presence of cataCXiumPtB, produced high yields of product at buffered pH 6.0; the yields dropped off precipitously at buffered pH 5.0 and lower. The fall-off in yield was attributed to the decomposition of the Pd-ligand complex due to the protonation of the ligand in the more acidic aqueous media. In contrast, in the absence of an added ligand, 4-amino-2-chloropyridine produced quantitative yields at buffered pH 3.5 and 4.5 while 4-amino-2-bromopyridine produced quantitative yields in a series of buffered media ranging from pH 4.5 to 1.5. These substrates are only partially protonated in acidic media and can behave as active Pd ligands in the Suzuki catalytic cycle.
- Li, Zhao,Gelbaum, Carol,Campbell, Zachary S.,Gould, Paul C.,Fisk, Jason S.,Holden, Bruce,Jaganathan, Arvind,Whiteker, Gregory T.,Pollet, Pamela,Liotta, Charles L.
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supporting information
p. 15420 - 15432
(2017/12/15)
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- A novel graphene-supported palladium catalyst for suzuki-miyaura coupling of less reactive heteroaryl halides in water
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An efficient reduced graphene oxide-supported heterogenized palladium complex with pyrene-tagged ketoiminato ligand has been developed and used for cross-coupling of less reactive heteroaryl halides in water. Desirable catalytic activity was observed with high (up to 98%) conversion of the less reactive reactants under relatively mild conditions. The efficiency and green nature of the catalyst were confirmed without significant loss of activity.
- Taher, Abu,Lee, Dong-Jin,Lee, Ik-Mo,Rahman, Md. Lutfor,Sarker, Md Shaheen
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p. 1478 - 1485
(2016/10/11)
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- Aqueous Suzuki Coupling Reactions of Basic Nitrogen-Containing Substrates in the Absence of Added Base and Ligand: Observation of High Yields under Acidic Conditions
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A series of aqueous heterogeneous Suzuki coupling reactions of substrates containing basic nitrogen centers with phenylboronic acid in the absence of added base and ligand is presented. High yields of products were obtained by employing aryl bromides containing aliphatic 1°, 2°, and 3° amine substituents, and good to high yields were obtained by employing a variety of substituted bromopyridines. In the former series, the pH of the aqueous phase changed from basic to acidic during the course of the reaction, while in the latter series the aqueous phase was on the acidic side of the pH scale throughout the entire course of reaction. A mechanistic interpretation for these observations, which generally preserves the oxo palladium catalytic cycle widely accepted in the literature, is presented.
- Li, Zhao,Gelbaum, Carol,Fisk, Jason S.,Holden, Bruce,Jaganathan, Arvind,Whiteker, Gregory T.,Pollet, Pamela,Liotta, Charles L.
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p. 8520 - 8529
(2016/09/28)
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- (Diphosphine)Nickel-catalyzed negishi cross-coupling: An experimental and theoretical study
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The use of a strongly donating "(bis-dialkylphosphine)Ni" fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni0/NiII cycle is operative in this system.
- Nicolas, Emmanuel,Ohleier, Alexia,D'Accriscio, Florian,Pécharman, Anne-Frédérique,Demange, Matthieu,Ribagnac, Philippe,Ballester, Jorge,Gosmini, Corinne,Mézailles, Nicolas
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supporting information
p. 7690 - 7694
(2015/05/20)
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- PYRROLIDINYL UREA, THIOUREA, GUANIDINE AND CYANOGUANIDINE COMPOUNDS AS TRKA KINASE INHIBITORS
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Compounds of Formula (I): or stereoisomers, tautomers, or pharmaceutically acceptable salts, or solvates or prodrugs thereof, where R1, R2, Ra, Rb, Rc, Rd, X, Ring B, and Ring C are as defined herein, and wherein Ring B moiety and the NH-C(=X)-NH moiety are in the trans configuration, are inhibitors of TrkA kinase and are useful in the treatment of diseases which can be treated with a TrkA kinase inhibitor such as pain, cancer, inflammation/inflammatory diseases, neurodegenerative diseases, certain infectious diseases, Sjogren's syndrome, endometriosis, diabetic peripheral neuropathy, prostatitis and pelvic pain syndrome.
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Paragraph 00577
(2014/06/11)
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- Co(acac)2/O2-mediated oxidative isocyanide insertion with 2-aryl anilines: Efficient synthesis of 6-amino phenanthridine derivatives
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A novel and efficient protocol for the creation of 6-amino phenanthridine derivatives by Co(acac)2-catalyzed isocyanide insertion with 2-aryl anilines under an O2 atmosphere via homolytic aromatic substitution (HAS) type C-H functionalization has been developed. This reaction not only proceeds smoothly utilizing O2 as the oxidant but also provides a new approach to construct phenanthridine derivatives utilizing readily available 2-aryl anilines with isocyanides instead of 2-isocyanobiaryls with different radical precursors.
- Zhu, Tong-Hao,Wang, Shun-Yi,Tao, Yang-Qing,Wei, Tian-Qi,Ji, Shun-Jun
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supporting information
p. 1260 - 1263
(2014/03/21)
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- NAPHTHALENE DERIVATIVE
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The present invention provides compounds which can regulate VCP activity. The present invention provides the compound of formula (I) (R is as defined in the description) or oxides, esters, prodrugs, pharmaceutically acceptable salts or solvates thereof. The compounds can regulate VCP activity, and thus are useful for treating VCP-mediated diseases such as neurodegenerative diseases.
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Paragraph 0350
(2013/06/27)
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- Ortho-(Dimesitylboryl)phenylphosphines: Positive boryl effect in the palladium-catalyzed suzuki-miyaura coupling of 2-chloropyridines
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Catalytic systems combining ortho-(dimesitylboryl) phenylphosphines and palladium precursors have been evaluated in the Suzuki-Miyaura couplings of chloro-N-heterocycles, in particular 2-chloro pyridines, with arylboronic acids. The Lewis basic character of the substrates does not interfere with the Lewis acidic site of the ligands, even for a substrate featuring free NH2 groups. The influence of several reaction parameters has been studied and the ortho-dimesitylboryl moiety was actually found to substantially enhance the catalytic performance. The role of this group has been examined using preformed phosphine-borane/Pd complexes and the formation of an original phosphine/h4-boratabutadiene complex has been identified as a possible deactivation pathway. Regioselective coupling of 2,6-dichloro-3-nitropyridine with phosphine-borane/Pd catalysts has also been explored, and sequential double cross-couplings were found to give a direct and efficient access to unsymmetrical 2,6-diarylpyridines.
- Malacea, Raluca,Chahdoura, Faouzi,Devillard, Marc,Saffon, Nathalie,Gomez, Montserrat,Bourissou, Didier
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p. 2274 - 2284
(2013/10/01)
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- First synthesis of benzopyridoiodolium salts and twofold Buchwald-Hartwig amination for the total synthesis of quindoline
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The first synthesis of cyclic benzopyridoiodolium salts is described. These hypervalent iodine intermediates are used in an efficient strategy for the construction of the -carboline core. This novel approach involves a twofold palladium-catalyzed Buchwald
- Letessier, Julien,Detert, Heiner
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p. 290 - 296
(2012/04/17)
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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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- Highly active and recyclable silica gel-supported palladium catalyst for mild cross-coupling reactions of unactivated heteroaryl chlorides
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Silica gel-supported β-ketoiminatophosphane-Pd complex (Pd@SiO 2) was shown to be a highly active and long-lived catalyst for aqueous Suzuki, Stille and Sonogashira coupling reactions of heteroaryl chlorides. A wide range of heteroaryl chlorides could be efficiently coupled with different nucleophilic partners in the presence of only 0.5 mol% catalyst and under mild conditions. This is one of the most powerful heterogeneous catalysts for the couplings of diverse heteroaryl chlorides. Furthermore, the catalyst could be reused with almost consistent activity. The Royal Society of Chemistry 2010.
- Lee, Dong-Hwan,Jung, Ji-Young,Jin, Myung-Jong
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experimental part
p. 2024 - 2029
(2011/02/22)
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- Expanded heterogeneous Suzuki-Miyaura coupling reactions of aryl and heteroaryl chlorides under mild conditions
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A mesoporous LTA zeolite (MP-LTA)-supported palladium catalyst was developed for the highly efficient Suzuki-Miyaura reaction of aryl and heteroaryl chlorides. The couplings of various aryl chlorides with arylboronic acids in aqueous ethanol were efficiently achieved in the presence of 1.0 mol% of the catalyst. Furthermore, the scope of this catalyst was extended to the coupling of heteroaryl chlorides. Regardless of the substituents, all of the coupling reactions were very clean and highly efficient under mild heating. It shows that our catalyst is one of the most powerful heterogeneous catalysts for the coupling of a wide range of aryl and heteroaryl chlorides. The catalyst could be repetitively used at least 10 times without a significant loss of its catalytic activity. Compared to mesoporous SBA-15 and MCM-41 materials, the MP-LTA support proved to be very stable and robust to prevent degradation upon reuse.
- Lee, Dong-Hwan,Choi, Minkee,Yu, Byung-Woo,Ryoo, Ryong,Taher, Abu,Hossain, Shahin,Jin, Myung-Jong
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supporting information; experimental part
p. 2912 - 2920
(2010/04/01)
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- New functionalised silicas for highly selective cation exchange SPE purification in medicinal chemistry
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Functionalised silicas 2 and 3 are effective for the cation exchange SPE purification of basic molecules containing acid-sensitive functionalities, the selective separations of mixtures of basic compounds and accelerated reaction work-ups/product isolatio
- Brown, Jane,Chighine, Alessandra,Colucci, Marie A.,Galaffu, Nicola,Hirst, Simon C.,Seymour, Helen M.,Shiers, Jason J.,Wilkes, Robin D.,Williams, Jonathan G.,Wilson, John R.H.
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p. 4968 - 4971
(2008/09/21)
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- Palladium-catalyzed cross-coupling reactions of pyridylboronic acids with heteroaryl halides bearing a primary amine group: Synthesis of highly substituted bipyridines and pyrazinopyridines
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(Chemical Equation Presented). A range of halogenated aromatics and heteroaromatics bearing a primary amine group are shown to be suitable substrates for Suzuki cross-coupling reactions with arylboronic acids and pyridylboronic acids under standard conditions, without the need for protection/deprotection steps. New amino-substituted arylpyridines, bipyridines, and pyrazinopyridines have thereby been obtained. Conditions for the efficient syntheses of 2-methoxy-5-pyridylboronic acid 1 and 2-methoxy-3-pyridylboronic acid 2 in ca. 75 g batches have been defined. A 2-fold reaction of 2-amino-5-bromopyrazine with 2,5-dimethoxy-1,4-benzenediboronic acid affords 1,4-dimethoxy-2,5-bis[2-(5-aminopyrazyl)]benzene 31. The X-ray crystal structures of 1 and 31·DMF are reported.
- Thompson, Amy E.,Hughes, Gregory,Batsanov, Andrei S.,Bryce, Martin R.,Parry, Paul R.,Tarbit, Brian
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p. 388 - 390
(2007/10/03)
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- Method for producing optical-active cis-piperidine derivatives
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An optical-active cis-piperidine derivative of high chemical purity and high optical purity is efficiently produced through optical resolution of a cis-piperidine derivative mixture, racemic cis-piperidine derivative with an optical-active tartaric acid d
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- Palladium Charcoal-Catalyzed Suzuki-Miyaura Coupling to Obtain Arylpyridines and Arylquinolines
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A phosphine ligand, such as PPh3 or 2-(dicyclohexylphosphino)biphenyl, is essential for the Pd/C-catalyzed Suzuki-Miyaura coupling of halopyridines and haloquinolines, although it has been reported that the reaction of phenyl chlorides can be catalyzed by nonprereduced Pd/C without any additives. In the reactions of bromopyridines, bromoquinolines, 2-chloropyridines, and 2-chloroquinolines, PPh3 was effective enough to provide coupling products in good yields. However, in the reactions of 3-chloropyridine, 4-chloropyridine, and 6-chloroquinoline, sterically hindered 2-(dicyclohexylphosphino)biphenyl was indispensable as a ligand.
- Tagata, Tsuyoshi,Nishida, Mayumi
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p. 9412 - 9415
(2007/10/03)
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- Process for preparing 2-phenyl-3-aminopyridine, substituted phenyl derivatives, thereof, and salts thereof
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A process for preparing 2-phenyl-3-aminopyridine, and substituted phenyl derivatives and salts thereof.
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- Preparation of substituted piperidines
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Substituted piperidines and related compounds of the formula STR1 wherein R1 and R2 are herein defined are disclosed.
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