- An Approach to Tetraphenylenes via Pd-Catalyzed C-H Functionalization
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Tetraphenylenes not only are theoretically and experimentally interesting but also have potential applications in a variety of fields such as materials science, supramolecular chemistry, and asymmetric catalysis. A facile and efficient approach is reported for the syntheis of tetraphenylene and its derivatives from 2-iodobiphenyls via Pd-catalyzed C-H activation. A range of substituted tetraphenylenes can be synthesized using this method, and the reaction can be performed on gram scale with relatively high efficiency, demonstrating its practical utility. This novel approach provides easy access to tetraphenylenes and should facilitate research on the application of this type of fascinating molecules.
- Jiang, Hang,Zhang, Yu,Chen, Dushen,Zhou, Bo,Zhang, Yanghui
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- Toward a continuous-flow synthesis of Boscalid
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A two-step continuous-flow protocol for the synthesis of 2-amino-4′-chlorobiphenyl, a key intermediate for the industrial preparation of the fungicide Boscalid is described. Initial tetrakis(triphenylphosphine)palladium-catalyzed high-temperature Suzuki-Miyaura cross-coupling of 1-chloro-2-nitrobenzene with 4-chlorophenylboronic acid in a microtubular flow reactor at 160°C using the tert-butanol/water/potassium tert-butoxide solvent/base system provides 4′-chloro-2-nitrobiphenyl in high yield. After in-line scavenging of palladium metal with the aid of a thiourea-based resin, subsequent heterogeneous catalytic hydrogenation is performed over platinum-on-charcoal in a dedicated continuous-flow hydrogenation device. The overall two-step homogeneous/heterogeneous catalytic process can be performed in a single operation providing the desired 2-amino-4′- chlorobiphenyl in good overall yield and high selectivity. Copyright
- Glasnov, Toma N.,Kappe, C. Oliver
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- Copper-Catalyzed Diphenylation of P(O)-OH Bonds with Cyclic Diaryliodonium Salts
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A copper-catalyzed diphenylation of P(O)?OH bonds with cyclic diaryliodonium salts is described. Valuable 2′-iodo substituted biaryl phosphinic/phosphoric acid esters were obtained in good to excellent yields, which could be further transformed to diversified building blocks for the synthesis of bioactive compounds, pharmaceuticals and functional materials.
- Wang, Gang,Xiong, Biquan,Zhou, Congshan,Liu, Yu,Xu, Weifeng,Yang, Chang-An,Tang, Ke-Wen,Wong, Wai-Yeung
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- Improved Suzuki-Miyaura reactions of aryldiazonium salts with boronic acids by tuning palladium on charcoal catalyst properties
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An improved Suzuki-Miyaura cross-coupling reaction of aryldiazonium tetrafluoroborates with boronic acids catalyzed by a highly active palladium catalyst supported on charcoal is described as an extremely practical and efficient protocol. A properties-activity study of various catalysts clearly established that the optimal catalytic activity was obtained with palladium nanoparticles having a low oxidation degree and uniformly dispersed on the charcoal. The optimized reaction conditions allow the cross-coupling to proceed at room temperature without any base and ligand in technical grade methanol. Although the catalyst could not be recycled, the low palladium contamination of the solvent and product after a simple filtration of the palladium on charcoal (Pd/C) renders the present protocol competitive and safer for the environment compared to more conventional homogeneous conditions. We have highlighted the efficiency of this novel protocol by a short synthesis of the fungicide Boscalid
- Felpin, Francois-Xavier,Fouquet, Eric,Zakri, Cecile
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- A Sustainable 1-Pot, 3-Step Synthesis of Boscalid Using Part per Million Level Pd Catalysis in Water
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Boscalid is an active ingredient in several fungicides marketed by the BASF. Literature approaches use multipot processes, organic solvents, and unsustainable levels of palladium catalysis. Herein is disclosed a 1-pot, 3-step route using nanomicelles in water as the reaction medium and a very low loading (700 ppm or 0.07 mol %) of costly and endangered Pd. The sequence developed involves an initial Suzuki-Miyaura cross-coupling, the product from which is not isolated. The second step relies on a carbonyl iron powder (CIP) reduction of the aryl nitro group, followed by the third and final step involving an acylation with the required 2-chloronicotinyl chloride. The overall isolated yield for these three steps is 83%.
- Takale, Balaram S.,Thakore, Ruchita R.,Mallarapu, Rushil,Gallou, Fabrice,Lipshutz, Bruce H.
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- Strongly Directing Substituents in the Radical Arylation of Substituted Benzenes
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Although general interest in radical arylation reactions has grown rapidly in recent years, poor regioselectivities and the need to use a large excess of the radical-accepting arene have hindered their application to substituted benzenes. We now describe experimental and computational investigations into the substituent effects that lead to regioselective addition based on the recent discovery of anilines as outstanding substrates for radical arylations.
- Hofmann, Josefa,Clark, Timothy,Heinrich, Markus R.
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- Indium powder as the reducing agent in the synthesis of 2-amino-1,1′-biphenyls
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An improved and simplified In-based protocol for the reduction of 2-nitro-1,1′-biphenyls to the corresponding 2-amino-1,1′-biphenyls is disclosed. The method utilizes only a stoichiometric quantity of indium powder as the reducing reagent along with a stoichiometric quantity of ammonium chloride. The work-up is very simple, it requires only a simple filtration of the post-reaction mixture whereupon the reaction medium is removed under reduced pressure. The method was also proven to operate with a variety of functional groups to provide high to excellent yields of the target 2-amino-1,1′-biphenyls. A proposal for a reaction mechanism is also provided.
- Elumalai, Vijayaragavan,Bj?rsvik, Hans-René
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- Regiospecific Introduction of Halogens on the 2-Aminobiphenyl Subunit Leading to Highly Potent and Selective M3 Muscarinic Acetylcholine Receptor Antagonists and Weak Inverse Agonists
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Muscarinic M3 receptor antagonists and inverse agonists displaying high affinity and subtype selectivity over the antitarget M2 are valuable pharmacological tools and may enable improved treatment of chronic obstructive pulmonary disease (COPD), asthma, or urinary incontinence. On the basis of known M3 antagonists comprising a piperidine or quinuclidine unit attached to a biphenyl carbamate, 5-fluoro substitution was responsible for M3 subtype selectivity over M2, while 3′-chloro substitution substantially increased affinity through a σ-hole interaction. Resultantly, two piperidinyl-and two quinuclidinium-substituted biphenyl carbamates OFH243 (13n), OFH244 (13m), OFH3911 (14n), and OFH3912 (14m) were discovered, which display two-digit picomolar affinities with Ki values from 0.069 to 0.084 nM, as well as high selectivity over the M2 subtype (46-to 68-fold). While weak inverse agonistic properties were determined for the biphenyl carbamates 13m and 13n, neutral antagonism was observed for 14m and 14n and tiotropium under identical assay conditions.
- Fischer, Oliver,Hofmann, Josefa,Rampp, Hannelore,Kaindl, Jonas,Pratsch, Gerald,Bartuschat, Amelie,Taudte, R. Verena,Fromm, Martin F.,Hübner, Harald,Gmeiner, Peter,Heinrich, Markus R.
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- An efficient water-soluble surfactant-type palladium catalyst for Suzuki cross-coupling reactions in pure water at room temperature
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A palladium catalyst based on a bidentate phosphine-type zwitterionic surfactant as a ligand exhibited an excellent catalytic activity in the Suzuki-Miyaura cross coupling reactions. This novel method allowed the reaction of aryl halides with arylboronic acids to occur in pure water at room temperature, forming a variety of biaryls in good to high yields. Heterobiaryls were also efficiently assembled even in the presence of water-insoluble heteroaryl halides as substrates. In addition, such a coupling protocol was successfully used in the iterative diarylation of 2,5-dibromopyridine in one-pot.
- Qiu, Pei,Zhao, Jing Yang,Shi, Xu,Duan, Xin Hong
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- Palladium Palladium Nanoparticles Nanoparticles Supported Supported on β-cyclodextrin on β-Cyclodextrin Functionalised Functionalized Poly(amido Poly(amidoamine)s amine)s and their and Application Their Application in Suzuki-Miyaura in Suzuki-Miyaura Cross-Coupling Cross-Coupling Reactions Reactions
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Herein, the synthesis, characterization and catalytic application of an organic-inorganic, palladium (Pd)-containing hybrid material, poly(amidoamine)-cyclodextrin (Pd@PAAs-CD), is reported as an efficient catalyst for Suzuki-Miyaura coupling reactions. The structure of Pd@PAAs-CD was confirmed by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), inductively-coupled plasma atomic emission spectroscopy (ICP-AES), and 1H nuclear magnetic resonance (NMR) spectroscopy. Furthermore, an efficient protocol has been developed using Pd@PAAs-CD as the catalyst in a Suzuki-Miyaura cross-coupling reaction in an aqueous medium in high yields. By using cyclodextrin (CD) as the mediator grafted onto PAAs, the Pd nanoparticles (NPs) were dispersed and enhanced the catalytic reaction by promoting host-guest interactions with the CD. In addition, the reusability of the Pd@PAAs-CD hybrid material is demonstrated for use in multiple sequential cross-coupling reactions.
- Zhang, Wei,Yao, Zi-Jian,Deng, Wei
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- Synthesis method of 2-bromo-4 '-chloro-1, 1'-biphenyl
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The invention belongs to the technical field of synthesis of compounds, and particularly discloses a synthesis method of 2-bromo-4 '-chloro-1, 1'-biphenyl. According to the method, aniline and parachloroiodobenzene are adopted as raw materials, an intermediate 1 is generated through a photocatalytic coupling reaction, and then the intermediate 1 is brominated through diazotization to obtain a final product. According to the method, expensive raw materials such as boric acid needed in the prior art are replaced with low-cost raw materials, the production cost is greatly reduced, and the method is energy-saving, environment-friendly, high in reaction yield in each step, simple in technological operation and suitable for technological amplification production.
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Paragraph 0009; 0025; 0027-0028; 0031; 0032-0033; 0037; ...
(2022/03/31)
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- Preparation method of acrylamido
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The present invention relates to a method for preparing a pyrimidine, 9-fluorenone as raw material, by open loop, acid chloride, amidation, chlorination, Hofmann (Hofmann) rearrangement degradation to give 2-(4'-chlorophenyl) aniline, and then condensed with 2-chloronicotinamide to give the product acetoimide, the present invention also relates accordingly to the intermediates 4'-chloro-2-bibenzamide and 4'-chloro-2-aminobiphenyl preparation method. The method of the present invention can obtain the target product with high yield, high purity, and can reduce costs while reducing environmental harm.
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- Pd-Catalysed Suzuki-Miyaura cross-coupling of aryl chlorides at low catalyst loadings in water for the synthesis of industrially important fungicides
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The Suzuki-Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis of crop protection-relevant active ingredients in water is disclosed. Optimisation of the reaction conditions allowed running the reaction with 50 ppm of Pd-catalyst loading without an additional organic solvent in the cross-coupling reaction step in short reaction times. The system was optimised for the initial cross-coupling step of the large scale produced fungicides Boscalid, Fluxapyroxad and Bixafen up to 97% yield. It is also shown that the Suzuki-Miyaura reaction can be easily scaled up to 50 g using a simple product separation and purification using environmentally benign solvents in the work-up. To show the usability of this method, it was additionally applied in the three-step synthesis of the desired active ingredients.
- Goetz, Roland,Hashmi, A. Stephen K.,Orecchia, Patrizio,Petkova, Desislava Slavcheva,Rominger, Frank,Schaub, Thomas
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p. 8169 - 8180
(2021/11/01)
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- Regioselective Radical Arene Amination for the Concise Synthesis ofortho-Phenylenediamines
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The formation of arene C-N bonds directly from C-H bonds is of great importance and there has been rapid recent development of methods for achieving this through radical mechanisms, often involving reactiveN-centered radicals. A major challenge associated with these advances is that of regiocontrol, with mixtures of regioisomeric products obtained in most protocols, limiting broader utility. We have designed a system that utilizes attractive noncovalent interactions between an anionic substrate and an incoming radical cation in order to guide the latter to the areneorthoposition. The anionic substrate takes the form of a sulfamate-protected aniline and telescoped cleavage of the sulfamate group after amination leads directly toortho-phenylenediamines, key building blocks for a range of medicinally relevant diazoles. Our method can deliver both free amines and monoalkyl amines allowing access to unsymmetrical, selectively monoalkylated benzimidazoles and benzotriazoles. As well as providing concise access to valuableortho-phenylenediamines, this work demonstrates the potential for utilizing noncovalent interactions to control positional selectivity in radical reactions.
- Gillespie, James E.,Morrill, Charlotte,Phipps, Robert J.
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supporting information
p. 9355 - 9360
(2021/07/19)
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- α-Bromoacrylic Acids as C1 Insertion Units for Palladium-Catalyzed Decarboxylative Synthesis of Diverse Dibenzofulvenes
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Herein α-bromoacrylic acids have been employed as C1 insertion units to achieve the palladium-catalyzed [4 + 1] annulation of 2-iodobiphenyls, which provides an efficient platform for the construction of diverse dibenzofulvenes. This protocol enables the formation of double C(aryl)-C(vinyl) bonds via a C(vinyl)-Br bond cleavage and decarboxylation. It is particularly noteworthy that the method features a broad substrate scope, and various interesting frameworks, such as bridged ring, fused (hetero)aromatic ring, and divinylbenzene, can be successfully incorporated into the products.
- Zhang, Minghao,Deng, Wenbo,Sun, Mingjie,Zhou, Liwei,Deng, Guobo,Liang, Yun,Yang, Yuan
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supporting information
p. 5744 - 5749
(2021/08/18)
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- Polymetallic magnetic palladium catalysts for the Suzuki reaction in aqueous media
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A mechanochemical method for the synthesis of Pd-Fe-Co-Ni ferromagnetic composites was developed. The composites are highly efficient catalysts for the Suzuki reaction in aqueous media. They can be easily removed with an external magnet and reused without losing catalytic activity.
- Bumagin, N. A.
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p. 1483 - 1488
(2021/09/04)
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- 4CzIPN-tBu-Catalyzed Proton-Coupled Electron Transfer for Photosynthesis of Phosphorylated N-Heteroaromatics
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2,4,5,6-Tetrakis(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile (4CzIPN-tBu) was developed as a photocatalyst for the phosphorus-radical-initiated cascade cyclization reaction of isocyanides. By using 4CzIPN-tBu as catalyst, we developed a visible-light-induced proton-coupled electron transfer strategy for the generation of phosphorus-centered radicals, via which a wide range of phosphorylated phenanthridines, quinolines, and benzothiazoles were successfully constructed.
- Liu, Yan,Chen, Xiao-Lan,Li, Xiao-Yun,Zhu, Shan-Shan,Li, Shi-Jun,Song, Yan,Qu, Ling-Bo,Yu, Bing
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supporting information
p. 964 - 972
(2021/01/12)
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- Scalable electrochemical synthesis of diaryliodonium salts
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Cyclic and acyclic diaryliodonium are synthesised by anodic oxidation of iodobiaryls and iodoarene/arene mixtures, respectively, in a simple undivided electrolysis cell in MeCN-HFIP-TfOH without any added electrolyte salts. This atom efficient process does not require chemical oxidants and generates no chemical waste. More than 30 cyclic and acyclic diaryliodonium salts with different substitution patterns were prepared in very good to excellent yields. The reaction was scaled-up to 10 mmol scale giving more than four grams of dibenzo[b,d]iodol-5-ium trifluoromethanesulfonate (>95%) in less than three hours. The solvent mixture of the large-scale experiment was recovered (>97%) and recycled several times without significant reduction in yield.
- Elsherbini, Mohamed,Moran, Wesley J.
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supporting information
p. 4706 - 4711
(2021/06/11)
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- Direct photoexcitation of benzothiazolines: Acyl radical generation and application to access heterocycles
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An acyl radical generation and functionalization strategy through direct photoexcitation of benzothiazolines has been developed. The formed acyl radical species can either be trapped by quinoxalin-2-ones to realize their C(3)-H functionalization or trigger a cascade radical cyclization with isonitriles to synthesise biologically important phenanthridines. The synthetic value of this protocol can be further illustrated by the modification of quinoxalin-2-ones, containing important natural products and drug-based complex molecules.
- He, Xiang-Kui,Li, Lei,Lu, Juan,Xuan, Jun,Ye, Hai-Bing
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supporting information
(2021/11/27)
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- Synthesis and process optimization of Boscalid by catalyst Pd-PEPPSI-IPrDtBu-An
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The purpose of this research was to reduce the amount of noble metal palladium catalyst and improve the catalytic performance in the Suzuki–Miyaura cross-coupling reaction, which is the key step in the synthesis of Boscalid. Taking o-bromonitrobenzene and p-chlorophenylboronic acid as raw materials, three kinds of Pd-PEPPSI-IPr catalysts were synthesized and employed in the Suzuki reaction, and then the biaryl product was subjected to reduction and condensation reaction to give Boscalid. Under the optimal reaction conditions, the result showed that the catalytic system exhibits highest catalytic efficiency under aerobic conditions, giving the 2-(4-chlorophenyl)nitrobenzene in over 99 % yield. Moreover, the Pd-PEPPSI-IPrDtBu-An catalyst was minimized to 0.01 mol%. The synthesis process was mild, the post-treatment was simple, and the production cost was reduced, which makes it suitable for industrial production.
- Xu, Jian,Lan, Xiao-Bing,Xia, Lin-Jian,Yang, Yi,Cao, Gao
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p. 247 - 256
(2021/05/06)
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- Synthesis method of boscalid intermediate 2-(4 '-chlorphenyl) aniline
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The invention discloses a synthesis method of boscalid intermediate 2-(4 '-chlorphenyl) aniline, and belongs to the technical field of pesticide intermediate synthesis. The 2-(4 '-chlorphenyl) anilineis prepared by taking 9-fluorenone as an initial raw material through ring opening, chlorination, acylating chlorination, ammonification and Hofmann degradation reaction. The preparation method avoids the use of an expensive metal catalyst, the initial raw material is cheap and easy to obtain, and the method has the characteristics of simple reaction operation and high yield, and has higher valuein industrial production.
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- Visible-Light-Induced Decarboxylative Cyclization/Hydrogenation Cascade Reaction to Access Phenanthridin-6-yl(aryl)methanol by an Electron Donor-Acceptor Complex
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A novel and efficient visible-light-induced decarboxylative cyclization/hydrogenation cascade reaction of α-oxocarboxylic acids and 2-isocyanobiaryls has been developed. Without the need of any external photosensitizer, oxidant, and reductant, this method offers a mild and green approach for the synthesis of diverse alcohols in moderate to good yields. A mechanism indicated that an electron donor-acceptor complex-driven decarboxylation, radical addition/cyclization, and in situ photochemical reduction of ketones to alcohols could be involved in the reaction.
- Shi, Wei,Ma, Fang,Li, Pinhua,Wang, Lei,Miao, Tao
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p. 13808 - 13817
(2020/11/20)
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- Visible-Light-Driven Difluoromethylation of Isocyanides with S-(Difluoromethyl)diarylsulfonium Salt: Access to a Wide Variety of Difluoromethylated Phenanthridines and Isoquinolines
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A highly efficient approach of visible-light-driven radical difluoromethylation of isocyanides to access a wide variety of difluoromethylated phenanthridines and isoquinolines is herein described. Electrophilic S-(difluoromethyl)diarylsulfonium salt proved to be a good difluoromethyl radical precursor under photoredox catalysis. A broad range of isocyanides were tolerated to furnish the corresponding difluoromethylated phenanthridines, isoquinolines, furo[3,2-c]pyridine, and pyrido[3,4-b]indole in moderate to excellent yields under mild conditions. A plausible mechanism was also proposed.
- Chen, Jia-Yi,Li, Xin,Lin, Li-Ting,Liu, Guo-Kai,Qin, Wen-Bing,Wong, Henry N. C.,Xiong, Wei
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p. 10479 - 10487
(2020/09/23)
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- Novel synthesis method of 4'-chloro-2-aminobiphenyl
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The invention discloses a novel synthesis method of 4'-chloro-2-aminobiphenyl. O-bromoaniline and p-chlorophenylboronic acid are used as initial raw materials. The preparation method comprises the following steps: putting o-bromoaniline, 1-2 equivalents of p-chlorophenylboronic acid, 1-3 equivalents of alkali and 1-2 mol% of a palladium catalyst into a reactor, adding water or a water-organic solvent mixed solution as a reaction solvent into the reactor, and carrying out stirring at 60-100 DEG C for 12-24 hours, after the reaction is finished, cooling the product to the room temperature, and extracting the solution by using an organic solvent, carrying out spin-drying to remove the organic solvent, and carrying out separation to obtain the product. The method has the advantages that 1) o-bromoaniline with a low price is used as a starting material, 2) a simple palladium salt is used as a catalyst, and ligand participation is not needed, 3) the method can be carried out in air without inert gas protection, 4) the method can be completed in water or a water phase system in one step, 5) the method is simple in post-treatment and can achieve separation of a product and a reaction system through simple organic solvent extraction, and 6) the method is high in yield of 4'-chloro-2-aminobiphenyl.
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Paragraph 0017-0034
(2020/05/02)
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- Mimics of Pincer Ligands: An Accessible Phosphine-Free N-(Pyrimidin-2-yl)-1,2-azole-3-carboxamide Framework for Binuclear Pd(II) Complexes and High-Turnover Catalysis in Water
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We report for the first time cyclic phosphine-free "head to tail"N,N,N pincer-like (pincer complexes mimicking) N-(pyrimidin-2-yl)-1,2-azole-3-carboxamide Pd(II) complexes with deprotonated amide groups as high-turnover catalysts (TON up to 106, TOF up to 1.2 × 107 h-1) for cross-coupling reactions on the background of up to quantitative yields under Green Chemistry conditions. The potency of the described catalyst family representatives was demonstrated in Suzuki-Miyaura, Mizoroki-Heck, and Sonogashira reactions on industrially practical examples. Corresponding ligands could be synthesized based on readily available reagents through simple chemical transformations. Within the complex structures, a highly unusual 1,3,5,7-tetraza-2,6-dipalladocane frame could be observed.
- Bumagin, Nikolay A.,Dikusar, Evgenij A.,Ivashkevich, Ludmila S.,Kletskov, Alexey V.,Kolesnik, Iryna A.,Lyakhov, Alexander S.,Petkevich, Sergey K.,Potkin, Vladimir I.
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supporting information
(2020/08/12)
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- Method for preparing 4'-chloro-2-aminobiphenyl
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The invention provides a preparation method of 4'-chloro-2-aminobiphenyl. The preparation method comprises the following steps: under the catalytic action of an N-heterocyclic carbene coordinated palladium complex containing a carbohydrate unit, carrying out cross-coupling reaction on 2-bromoaniline and 4-chlorophenylboronic acid to generate 4'-chloro-2-aminobiphenyl. The method according to the present invention is characterized in that an N-heterocyclic carbene coordinated palladium complex, which contains an alpha-D-altropyranose, a beta-D-altropyranose, an alpha-D-idopyranose or a beta-D-idopyranose carbohydrate unit and in which an imidazolyl nitrogen atom is linked to the 2-position or 3-position of a pyranoid ring, is used as a catalyst.
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Paragraph 0018
(2020/05/05)
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- Highly efficient palladium-catalyzed cross-coupling of diarylborinic acids with arenediazoniums for practical diaryl synthesis
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A highly efficient cross-coupling of cost-effective diarylborinic acids with both isolatable and latent arenediazoniums, i.e. tetrafluoroborates and aryltriazenes, respectively, has been developed with a practical palladium catalyst system under base-free conditions in open flask at room temperature. A variety of electronically and sterically various biaryls, in particular, those bearing a coordinative ortho-substituent, could be obtained in good to excellent yields by using 0.3 mol% palladium acetate as catalyst. Features of the protocol including cost-effectiveness of diarylborinic acids, efficacy to heteroatom ortho-substituted substrates and high chemoselectivity to aryl chlorides have been clearly demonstrated in practical synthesis of fungicide Boscalid.
- Wang, Fengze,Wang, Chen,Sun, Guoping,Zou, Gang
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supporting information
(2019/12/25)
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- Regiospecific Introduction of Halogens on the 2-Aminobiphenyl Subunit Leading to Highly Potent and Selective M3 Muscarinic Acetylcholine Receptor Antagonists and Weak Inverse Agonists
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Muscarinic M3 receptor antagonists and inverse agonists displaying high affinity and subtype selectivity over the antitarget M2 are valuable pharmacological tools and may enable improved treatment of chronic obstructive pulmonary disease (COPD), asthma, or urinary incontinence. On the basis of known M3 antagonists comprising a piperidine or quinuclidine unit attached to a biphenyl carbamate, 5-fluoro substitution was responsible for M3 subtype selectivity over M2, while 3′-chloro substitution substantially increased affinity through a σ-hole interaction. Resultantly, two piperidinyl- A nd two quinuclidinium-substituted biphenyl carbamates OFH243 (13n), OFH244 (13m), OFH3911 (14n), and OFH3912 (14m) were discovered, which display two-digit picomolar affinities with Ki values from 0.069 to 0.084 nM, as well as high selectivity over the M2 subtype (46-to 68-fold). While weak inverse agonistic properties were determined for the biphenyl carbamates 13m and 13n, neutral antagonism was observed for 14m and 14n and tiotropium under identical assay conditions.
- Fischer, Oliver,Hofmann, Josefa,Rampp, Hannelore,Kaindl, Jonas,Pratsch, Gerald,Bartuschat, Amelie,Taudte, R. Verena,Fromm, Martin F.,Hübner, Harald,Gmeiner, Peter,Heinrich, Markus R.
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p. 4349 - 4369
(2020/06/08)
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- Method for preparing boscalid
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The invention relates to a method for preparing boscalid. The method comprises the following steps: sequentially preparing intermediates 2-(4-chlorophenyl)aniline and 2-chloronicotinyl chloride by means of a chlorination/ring opening reaction, an amidation reaction, Hofmann rearrangement and an acylating chlorination reaction, and enabling the obtained intermediates to be subjected to a syntheticreaction to obtain the boscalid. The method for preparing the boscalid has the advantages of being easy in obtaining of raw materials, easy in creation of reaction conditions, little in environmentalpollution and high in yield, thus being suitable for large-scale production.
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- Synthesis process of 2-(4-chlorophenyl)aniline
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The invention discloses a synthesis process of 2-(4-chlorophenyl)aniline. The process adopts 9-fluorenone as a raw material, and uses four steps of ring opening, chlorination, amide amination and rearrangement degradation to obtain 2-(4-chlorophenyl) aniline. The process avoids the use of expensive raw materials and catalysts, and greatly reduces production costs. The content of the 2-(4-chlorophenyl)aniline prepared by the synthesis process is over 98%, and the total yield is over 75%.
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- Rhodium(I)-Catalyzed Aryl C-H Carboxylation of 2-Arylanilines with CO2
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An unprecedented Rh(I)-catalyzed, amino-group-assisted C-H carboxylation of 2-arylanilines with CO2 under redox-neutral conditions has been developed. This reaction was promoted by a phosphine ligand with t-BuOK as the base and did not require the use of additional strong organometallic reagent. It enabled an efficient direct conversion of a broad range of 2-(hetero)arylanilines including electron-deficient heteroarenes to various phenanthridinones. Possible intermediates of the reaction were also evaluated in the preliminary mechanistic studies.
- Gao, Yuzhen,Cai, Zhihua,Li, Shangda,Li, Gang
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supporting information
p. 3663 - 3669
(2019/05/17)
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- Visible-light-induced tandem radical addition-cyclization of 2-aryl phenyl isocyanides catalysed by recyclable covalent organic frameworks
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A visible-light-induced tandem radical addition-cyclization sequence via 2-aryl phenyl isocyanides as the starting material and two-dimensional covalent organic frameworks (2D-COFs) as the photocatalyst was developed, delivering multifarious 6-substituted phenanthridines in high yields. Benefitting from the utilization of a heterogeneous photocatalyst, this protocol features easy catalyst separation and excellent recyclability. A negligible loss of the catalytic activity was observed after multiple runs. High practicability of this protocol was further demonstrated by continuous flow experiments.
- Liu, Shuyang,Pan, Wenna,Wu, Songxiao,Bu, Xiubin,Xin, Shigang,Yu, Jipan,Xu, Hao,Yang, Xiaobo
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supporting information
p. 2905 - 2910
(2019/06/17)
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- Metal- and additive-free cascade trifluoroethylation/cyclization of organic isoselenocyanates by phenyl(2,2,2-trifluoroethyl)iodonium triflate
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A novel and convenient cascade trifluoroethylation/cyclization of organic isoselenocyanates by phenyl(2,2,2-trifluoroethyl)iodonium triflate is reported. A series of 2-isoselenocyanobiaryls and aryl alkyl isoselenocyanates reacted with phenyl(2,2,2-trifluoroethyl)iodonium triflate in CH2Cl2 at 40 °C under metal- and additive-free conditions for 3 h to provide the corresponding trifluoroethylselenolated phenanthridines and 3,4-dihydroisoquinoline derivatives in good to excellent yields. The reaction represents the first general approach to access trifluoroethylselenolated phenanthridines and 3,4-dihydroisoquinolines from organic isoselenocyanates.
- Zhao, Cheng-Long,Shi, Jin,Lu, Xiuqiang,Wu, Xun,Zhang, Cheng-Pan
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supporting information
(2019/09/03)
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- N-Heterocarbene Palladium Complexes with Dianisole Backbones: Synthesis, Structure, and Catalysis
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A series of palladium N-heterocyclic carbenes (NHCs), complexes C1-C5, bearing dianisole backbones and substituted N-aryl moieties have been synthesized and characterized. The electronic effect as well as the steric environment of the NHC ligands has been assessed. The synthesized palladium complexes were applied for Suzuki-Miyaura cross-coupling reactions under aerobic conditions. The relationship between the catalytic structure and catalytic performance was then extensively investigated. Upon optimizing the reaction conditions, the C4 was found to be highly efficient to catalyze the cross-coupling of (hetero)aryl chlorides with (hetero)arylboronic acids at a 0.1 mol % palladium loading.
- Li, Dong-Hui,He, Xu-Xian,Xu, Chang,Huang, Fei-Dong,Liu, Ning,Shen, Dong-Sheng,Liu, Feng-Shou
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p. 2539 - 2552
(2019/06/17)
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- Visible-Light-Promoted, Catalyst-Free Gomberg-Bachmann Reaction: Synthesis of Biaryls
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Biaryls were synthesized via a novel visible-light-promoted Gomberg-Bachmann reaction that does not require a photosensitizer or any metal reagents. The formation of an electron donor-acceptor complex between aryl diazonium salts and pyridine allows, under visible-light irradiation, the synthesis of biaryls in moderate-to-high yields.
- Lee, Juyoung,Hong, Boseok,Lee, Anna
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p. 9297 - 9306
(2019/08/12)
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- A new,: Substituted palladacycle for ppm level Pd-catalyzed Suzuki-Miyaura cross couplings in water
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A newly engineered palladacycle that contains substituents on the biphenyl rings along with the ligand HandaPhos is especially well-matched to an aqueous micellar medium, enabling valued Suzuki-Miyaura couplings to be run not only in water under mild conditions, but at 300 ppm of Pd catalyst. This general methodology has been applied to several targets in the pharmaceutical area. Multiple recyclings of the aqueous reaction mixture involving both the same as well as different coupling partners is demonstrated. Low temperature microscopy (cryo-TEM) indicates the nature and size of the particles acting as nanoreactors. Importantly, given the low loadings of Pd invested per reaction, ICP-MS analyses of residual palladium in the products shows levels to be expected that are well within FDA allowable limits.
- Takale, Balaram S.,Thakore, Ruchita R.,Handa, Sachin,Gallou, Fabrice,Reilly, John,Lipshutz, Bruce H.
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p. 8825 - 8831
(2019/10/16)
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- Nitrogen-Iodine Exchange of Diaryliodonium Salts: Access to Acridine and Carbazole
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A nitrogen-iodine exchange protocol of diaryliodonium salts with sodium azide salt is developed for general construction of significant functional acridines and carbazoles, in which introduction of nitrogen at a late stage was successfully established avoiding heteroatom incompatibility. Inorganic sodium azide served as the sole nitrogen atom source in this transformation. The diversiform functional acridines and carbazoles were comprehensively achieved through annulated diaryliodonium salts, respectively. Notably, Acridine orange (a fluorescent indicator for cell lysosomal dye) and Carprofen (a nonsteroidal anti-inflammatory drug) were efficiently established through this protocol.
- Wang, Ming,Fan, Qiaoling,Jiang, Xuefeng
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supporting information
p. 216 - 219
(2018/01/17)
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- Broad activity of diphenyleneiodonium analogues against Mycobacterium tuberculosis, malaria parasites and bacterial pathogens
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In this study, a structure-activity relationship (SAR) compound series based on the NDH-2 inhibitor diphenyleneiodonium (DPI) was synthesised. Compounds were evaluated primarily for in vitro efficacy against Gram-positive and Gram-negative bacteria, commonly responsible for nosocomial and community acquired infections. In addition, we also assessed the activity of these compounds against Mycobacterium tuberculosis (Tuberculosis) and Plasmodium spp. (Malaria). This led to the discovery of highly potent compounds active against bacterial pathogens and malaria parasites in the low nanomolar range, several of which were significantly less toxic to mammalian cells.
- Nguyen, Nghi,Wilson, Danny W.,Nagalingam, Gayathri,Triccas, James A.,Schneider, Elena K.,Li, Jian,Velkov, Tony,Baell, Jonathan
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p. 507 - 518
(2017/12/26)
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- Metal-Oxidant-Free Cobalt-Catalyzed C(sp2)-H Carbonylation of ortho-Arylanilines: An Approach toward Free (NH)-Phenanthridinones
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A traceless directing group assisted Co-catalyzed C(sp2)-H carbonylation of ortho-arylanilines for the synthesis of free (NH)-phenanthridinones in metal-based-oxidant-free fashion was accomplished. This protocol employs diisopropyl azodicarboxylate as the CO source and oxygen as the sole oxidant, and provides good yields with various functional tolerance. The methodology has been applied for the total synthesis of PARP inhibitor PJ-34. Furthermore, the kinetic isotopic effect experiments reveal the C-H bond cleavage probably occurred in the rate-determining step.
- Ling, Fei,Zhang, Chaowei,Ai, Chongren,Lv, Yaping,Zhong, Weihui
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p. 5698 - 5706
(2018/05/23)
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- Palladium/Norbornene Chemistry: Synthesis of Norbornene-Containing Arylsilanes Involving Double C-Si Bond Formation
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A novel palladium-catalyzed three-component cascade reaction of aryl halides with norbornene and hexamethyldisilane has been described, which allows the simultaneous construction of two C-Si bonds and one C-C bond. The method achieves ortho C-H functionalization of aryl halides through the formation of the five-membered palladacycle, leading to norbornene-containing arylsilanes.
- Xu, Yankun,Liu, Xiaodong,Chen, Wenqi,Deng, Guobo,Liang, Yun,Yang, Yuan
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p. 13930 - 13939
(2018/11/30)
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- Electrochemical initiation of electron-catalyzed phenanthridine synthesis by trifluoromethylation of isonitriles
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The electron-catalyzed formation of phenanthridines starting from isonitriles initiated by an electrochemical reduction of the Togni reagent is presented. The required number of faradays per mole of starting material and the respective yields clearly show the catalytic character of the electron in this reaction. The mechanism is supported by cyclic voltammetry experiments.
- Lübbesmeyer,Leifert,Sch?fer,Studer
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supporting information
p. 2240 - 2243
(2018/03/06)
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- A Co2B Mediated NaBH4 Reduction Protocol Applicable to a Selection of Functional Groups in Organic Synthesis
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A high-yielding and high-rate reduction method that operates with alkenes, alkynes, azides, nitriles, and nitroarenes was developed and optimized. The method makes use of sodium borohydride reduction of CoSO4 under release of hydrogen along with the formation of Co2B as a nanoparticle material. The produced Co2B activates the various functional groups for hydride reduction. The protocol was proven to operate with an assortment of functional groups to provide good to excellent yields. Furthermore, the reduction method was successfully adapted, implemented, and developed for a continuous flow approach using the multi-jet oscillating disk (MJOD) flow reactor platform at atmospheric pressure.
- Lundevall, Frida Johanne,Elumalai, Vijayaragavan,Drageset, Audun,Totland, Christian,Bj?rsvik, Hans-René
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supporting information
p. 3416 - 3425
(2018/07/29)
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- A dingding acid radical fungus amine synthesis process
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The invention relates to a technical field of chemical synthesis, in particular to a process for synthesizing dingding acid radical fungus amine, to chlorine monobromo-benzene and O-such as nitrobenzene raw material through the reaction, layered, desolvation, filtering and washing such as synthetic dingding acid radical fungus amine a plurality of steps, compared with the prior art, beneficial effect of the invention: this invention adopts the synthetic route to the routine by reaction of the chemical reaction, mild reaction conditions, the operation is simple, and is suitable for industrial; at the same time to the chlorine monobromo-benzene as raw materials are synthetic dichlorobenzothiazole boric acid, 2 - (4 - chlorophenyl) nitrobenzene, 2 - (4 - chlorophenyl) aniline and dingding acid radical fungus amine synthetic route, higher yields.
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Paragraph 0012
(2019/01/07)
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- An Active Palladium Colloidal Catalyst for the Selective Oxidative Heterocoupling of (Hetero)Aryl Boronic Acids
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A highly selective oxidative heterocoupling protocol for (hetero)aryl boronic acids with an active palladium colloidal catalyst was developed. The judicious choice of electronically different aryl boronic acids made possible such couplings under mild conditions, with air as oxidant, while embracing a wide substrate scope. This successful approach further allowed the development of a unique one-pot sequential oxidative heterocoupling/Suzuki–Miyaura cross-coupling tandem process for accessing substituted terphenyls.
- Sable, Vaibhav,Maindan, Karan,Bhilare, Shatrughn,Chrysochos, Nicolas,Schulzke, Carola,Kapdi, Anant R.
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supporting information
p. 2489 - 2498
(2018/09/10)
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- Method for preparing 4'-chloro-2-aminobiphenyl
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The invention provides a method for preparing 4'-chloro-2-aminobiphenyl, which comprises: carrying out coupling by using p-chlorophenyl magnesium halide (III) and chlorobenzonitrile (II) as raw materials and using manganese salt as a catalyst to obtain 4'-chloro-2-cyanobiphenyl (IV); carrying out mixed hydrolysis on the 4'-chloro-2-cyanobiphenyl (IV) and alkali as well as hydrogen peroxide to obtain 4'-chloro-2-amido biphenyl (V); carrying out Hofmann degradation on the obtained 4'-chloro-2-amido biphenyl (V) to obtain the 4'-chloro-2-aminobiphenyl (I). The method disclosed by the invention has the characteristics of operation safety and good economic feasibility, and is suitable for industrial development.
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Paragraph 0034; 0035
(2018/07/30)
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- A method for preparing substituted biphenyl
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The invention discloses a preparation method of substituted biphenyl. The preparation method includes the steps that under the anhydrous condition, a compound 2 and a compound 3 are subjected to a coupled reaction in solvent in the presence of Ni salt and ZnX3X4, and then substituted biphenyl is obtained, wherein Ni salt is one or more of NiX5X6(PPh3)2, NiX7X8(dppp), NiX9X10(dppf), NiX11X12(dppe) and acetylacetone nickel, the temperature of the coupled reaction is 0-30 DEG C, and ZnX3X4 is mixed with the compound 3 before the compound 2 is mixed with the compound 3. According to the method, reaction conditions are mild, the process is simple, operation is safe, requirements for equipment are low, aftertreatment is simple, pollution to the environment is small, industrial production is easy, the usage quantity of zinc halides is small, the cost is low, the yield is high, and the product purity is high.
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Paragraph 0124; 0127; 0128
(2018/08/03)
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- A dingding acid radical fungus amine intermediate preparation production pilot system (by machine translation)
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The utility model discloses a process for preparing intermediate dingding acid radical fungus amine production pilot system, the states the bromine chlorobenzene raw material cavity and O-nitro-chlorobenzene in raw material cavity communicated with the outside of the common discharge end is connected with the reactor, the states the bromine chlorobenzene raw material cavity and O-nitro-chlorobenzene mixed reactant in raw material cavity is connected with the output terminal of the intermediate the outside of the collecting and storing device, the intermediate collecting and storing device is connected with the output end of the quality and the stability of the measuring device, the quality and the stability of the output end of the measuring device for the precision measurement device, the accuracy of the measuring device is connected to the result output the results of the outside of the preferred finishing equipment and the reaction conditions gradually changing equipment. The dingding acid radical fungus amine intermediate preparation production pilot system through laboratory and amplifying pilot study, to pilot technology of improvement and innovation, formed a complete set of, high yield low-cost, high-quality, more in line with the requirements of environmental protection of the pilot operating system, to meet the requirement of the preparation. (by machine translation)
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Paragraph 0014; 0015
(2017/07/20)
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- A unified strategy for silver-, base-, and oxidant-free direct arylation of C-H bonds
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Here, we report a dual catalytic approach for room temperature direct arylation of C-H bonds with aryldiazonium salts as a simple aryl group donor, also working as an internal oxidant via C-N2 bond cleavage. This unified strategy has been achieved by the synergistic combination of visible-light metal-free photoredox and palladium catalysis under silver-, base- and/or additive-free conditions. The broad substrate scope, functional group tolerance, excellent regioselectivity and redox-neutral conditions of this process make it attractive for the effective synthesis of a wide range of important N-heterocyclic commodities such as dibenzo[b,d]azepine, carbazole and phenanthridine.
- Sahoo, Manoj K.,Midya, Siba P.,Landge, Vinod G.,Balaraman, Ekambaram
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supporting information
p. 2111 - 2117
(2017/07/24)
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- Photochemical intramolecular amination for the synthesis of heterocycles
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Polycyclic heterocycles can be formed in good to excellent yields via photochemical conversion of the corresponding substituted aryl azides under irradiation with purple LEDs in a continuous flow reactor. The experimental set-up is tolerant to UV-sensitive functional groups while affording diverse carbazoles, as well as an indole and pyrrole framework, in short reaction times. The photochemical method is presumed to progress through a mechanism differing from the other methods of azide activation involving transition metal catalysis.
- Parisien-Collette, Shawn,Cruché, Corentin,Abel-Snape, Xavier,Collins, Shawn K.
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supporting information
p. 4798 - 4803
(2017/10/23)
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- A field-based disparity analysis of new 1,2,5-oxadiazole derivatives endowed with antiproliferative activity
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A series of 1,2,5-oxadiazoles were synthesized as new potential antiproliferative agents. The in vitro cytotoxic activity evaluation of title compounds through MTT assay revealed that some of them showed significant activity against the HCT-116 cancer cell line. The field-based disparity analysis provided indications about the electrostatic, hydrophobic, and shape features underlying the cytotoxicity, suggesting that increasing the negative electrostatic field on the heterocyclic core of the structure has positive effects on the activity. The structure–activity relationships (SAR) around a particular compound can be explained allowing for a structural rationale for the differences in activity. The SAR provided by this series of compounds can be exploited to carry out further lead optimization.
- Porta, Federica,Gelain, Arianna,Barlocco, Daniela,Ferri, Nicola,Marchianò, Silvia,Cappello, Valentina,Basile, Livia,Guccione, Salvatore,Meneghetti, Fiorella,Villa, Stefania
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p. 820 - 839
(2017/10/03)
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- Visible-light-mediated radical insertion/cyclization cascade reaction: Synthesis of phenanthridines and isoquinolines from isocyanides
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A visible-light promoted single electron oxidation of ether enabled by photoredox catalysis has been accomplished. This procedure initiates a novel radical insertion/cyclization cascade reaction to generate phenanthridines and isoquinolines from easily available isocyanides under mild reaction conditions.
- Feng, Shangbiao,Li, Tao,Du, Chenglong,Chen, Peng,Song, Dengpeng,Li, Jinlai,Xie, Xingang,She, Xuegong
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supporting information
p. 4585 - 4588
(2017/04/28)
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- Preparation method of boscalid
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The invention discloses a preparation method of boscalid. The method comprises the following steps: preparation of a 2-(4-chlorphenyl) aniline intermediate, namely dissolving chlorophenylboronic acid, o-iodoaniline, benzaldehyde and a catalyst into a first solvent, stirring, adding a sodium carbonate solution for reflux reaction, cooling, standing and layering to obtain an organic phase, adding an acid to the obtained organic phase, standing, layering, adjusting the pH value of the organic phase by using alkali, carrying out extraction through an extraction agent, drying through a drying agent, concentrating the first solvent and re-crystallizing to obtain the 2-(4-chlorphenyl) aniline; and preparation of the boscalid, namely dissolving the 2-(4-chlorphenyl) aniline intermediate and triethylamine into a second solvent to obtain a mixed solution, slowly adding the organic solvent of 2-chloronicotinoyl chloride to the mixed solution at a room temperature, separating out the organic phase, evaporating the second solvent from filtrate, obtaining a crude product and re-crystallizing to obtain the boscalid. The method has the advantages of being short in reaction route, simple in operation and high in yield.
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Paragraph 0017; 0019
(2017/10/22)
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- Synthesis of zwitterionic palladium complexes and their application as catalysts in cross-coupling reactions of aryl, heteroaryl and benzyl bromides with organoboron reagents in neat water
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N-(3-Chloro-2-quinoxalinyl)-N′-arylimidazolium salts (aryl = 2,6-diisopropylphenyl [HL1Cl]Cl, aryl = mesityl [HL2Cl]Cl) have been synthesized by treating 2,3-dichloroquinoxaline with the corresponding N′-arylimidazole in neat water. Facile reactions of these imidazolium salts with Pd(PPh3)4 and Pd2(dba)3/PPh3 (dba = dibenzyledene acetone) at 50 °C have afforded zwitterionic palladium(ii) complexes [Pd(HL1)(PPh3)Cl2] (I) and [Pd(HL2)(PPh3)Cl2] (II) in excellent yields. I and II have been tested for their ability to catalyze Suzuki-Miyaura cross coupling (SMC) reactions in neat water/K2CO3 and are found to be highly active for carrying out these reactions between aryl bromides and organoboron reagents. Furthermore, the scope of the catalyst I was also examined by employing (hetero)aryl bromides, hydrophilic aryl bromides, benzyl bromides and various organoboron reagents. More than 80 aryl/benzyl bromide-arylboronic acid combinations were screened in neat water/K2CO3 and it was found that I was a versatile catalyst, which produced biaryls/diarylmethanes in excellent yields. A TON of 82 000 was achieved by using I. Studies on the mechanism have also been carried out to investigate the involvement of carbene complexes in the catalytic path. Poison tests and a two-phase test were also conducted and the results are reported.
- Ramakrishna,Dastagiri Reddy
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supporting information
p. 8598 - 8610
(2017/07/12)
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- Palladium-Catalyzed Synthesis of Tetrasubstituted Olefins by Triple Domino Process
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An efficient, highly regio- and stereoselective protocol for the synthesis of tetrasubstituted olefins was developed to take place by a palladium(0)-catalyzed triple domino process. It involves the formation of three new C?C bonds through double carbopalladation and C?H activation across 2-bromoaryl alkynyl biaryls/heteroaryls with norbornene. This method is practically simple with broad substrate scope and tolerates a wide range of substituents. The products bearing 9H-pyrrolo[1,2-a]indole motifs reveal intriguing solid state fluorescence properties and thus form a new class of aggregation induced emission (AIE) fluorophores. (Figure presented.).
- Naveen, Kanagaraj,Nikson, Savariyappan Albert,Perumal, Paramasivan Thirumalai
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supporting information
p. 2407 - 2413
(2017/07/22)
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- Pd/Cu-Catalyzed aerobic oxidative aromatic C-H bond activation/N-dealkylative carbonylation towards the synthesis of phenanthridinones
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It is important to achieve diverse functionalization of tertiary anilines due to their importance in biological molecules, pharmaceutical, functional materials, and ligands. A straightforward Pd/Cu-catalyzed oxidative C-H bond activation/N-dealkylative carbonylation of tertiary [1,1′-biphenyl]-2-anilines towards the synthesis of various biologically important phenanthridin-6(5H)-ones has been developed. A wide range of functional groups are well tolerated in this transformation. Moreover, O2 is utilized as the terminal oxidant to promote the oxidative carbonylation process.
- Shi, Renyi,Niu, Huiying,Lu, Lijun,Lei, Aiwen
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p. 1908 - 1911
(2017/02/10)
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- AgI-Promoted Difluoromethylation of Isocyanides To Give Difluoromethylated Phenanthridines
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An AgI-mediated ethoxycarbonyldifluoromethylation of isocyanides has been developed. This radical cascade reaction involves the addition of difluoromethylene radical to the isocyanide functionality, and subsequent homolytic aromatic substitution to give difluoromethylated phenanthridines with a good functional-group tolerance.
- Wan, Wen,Xu, Xiaochen,Chen, Yunrong,Jiang, Haizhen,Wang, Yong,Deng, Hongmei,Hao, Jian
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supporting information
p. 3145 - 3151
(2017/06/21)
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