- An easily available N-heterocyclic carbene–palladium(II) catalyst for Buchwald–Hartwig amination of aryl chlorides
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Abstract: An easily available N-heterocyclic carbene–palladium(II) complex was found to be an efficient catalyst for the Buchwald–Hartwig amination of aryl chlorides. Both secondary and primary amines were tolerated under the same reaction conditions. Under the optimal conditions, all reactions proceeded successfully to give the desired products in good to high yields within hours. Graphical Abstract: [Figure not available: see fulltext.]
- Wang, Tao,Xu, Kai,Liu, Lantao,Xie, Huanping,Li, Ying,Zhao, Wen-Xian
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- CuII-β-cyclodextrin complex as a nanocatalyst for the homo-and cross-coupling of arylboronic acids under ligand-and base-free conditions in air: Chemoselective cross-coupling of arylboronic acids in water
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We report here the transition-metal-catalyzed chemoselective cross-coupling of arylbroronic acids in high yields without using ligand or base. We have developed an efficient copper-catalyzed protocol for the homocoupling and cross-coupling of arylboronic acids. The protocol is also suitable for the cross-coupling of aliphatic primary amines with arylboronic acids. Aminophenols and primary amines bearing an alcoholic substituent on the aliphatic chain were coupled with arylboronic acids, and the products were obtained with high C-N coupling selectivity. An effective catalyst was Cu2-β- cyclodextrin, which is readily available and structurally simple, but has not previously been explored as a catalyst.
- Kaboudin, Babak,Abedi, Yaghoub,Yokomatsu, Tsutomu
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- Copper-TBAF catalyzed arylation of amines and amides with aryl trimethoxysilane
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A copper-catalyzed C-N bond forming reaction among aryl siloxane and primary, secondary amines as well as amides has been described. The reaction was conducted in the presence of P(C6F5)3 and 4 A molecular sieves in CHsub
- Lin, Baoda,Liu, Miaochang,Ye, Zhishi,Ding, Jinchang,Wu, Huayue,Cheng, Jiang
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- Palladium-Catalyzed N-Arylation of Amines and Amides with Aryltrimethylgermanes
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Described herein is a novel palladium-catalyzed C-N bond-formation reaction employing aryltrimethylgermanes as the new arylating reagents. Primary/secondary amines or even amides could be smoothly arylated to provide the corresponding N-arylation products in moderate to excellent yields.
- Zhang, Qiang,Liu, Cunfang,Shi, Juan,Xu, Qiong,Jin, Lingxia,Zhao, Chaibin,Zhang, Tianlei
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- Palladium-Catalyzed Amination of Aryl Halides: Mechanism and Rational Catalyst Design
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Palladium complexes of tri-o-tolyl phosphine and bis(diphenylphospino)ferrocene catalyze the reaction between aryl halides and either tin amides or amines in the presence of base to form aryl amines by halide substitution. This account describes our mechanistic and synthetic studies related to the amination reactions. These studies include kinetic behavior of the catalytic systems as well as direct observation of the primary stoichiometric reactions comprising the catalysis - including the rare C-N bond-forming reductive eliminations - and the mechanisms of these individual reactions. This paper also describes the development of tin-free amide sources and second generation amination catalysts that have resulted from our mechanistic understanding of the amination chemistry.
- Hartwig, John F.
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- Improved synthesis of 2-methoxyphenothiazine
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A procedure for synthesis of 2-methoxyphenothiazine (1) has been developed, starting from resorcinol and aniline by condensation, following methylation and cyclization. p-Toluenesulfonic acid and polysubstituted aromatics were employed as the catalyst of condensation and the solvent of cyclization, respectively, to improve the yield. The use of parallel experiments, statistical experimental design, and multivariate modeling made the total yield of the procedure as high as 74.2%. Copyright
- Ruan, Jian-Cheng,Zhang, Tao,Wang, Shuai,Liu, Jin-Qiang,Qian, Chao,Chen, Xin-Zhi
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- Facile N-Arylation of Amines and Sulfonamides
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(Matrix presented) A facile, transition-metal-free N-arylation procedure for amines and sulfonamides has been developed, which affords good to excellent yields of arylated products under very mild reaction conditions. A methoxy-substituted aryl triflate affords N-arylated products in high yields with excellent regioselectivity. This chemistry tolerates a variety of functional groups.
- Liu, Zhijian,Larock, Richard C.
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- Copper-mediated aryl amination: In situ generation of an active copper(I) species
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We have developed novel conditions for copper-mediated aryl amination by using a combination of easy-to-handle and inexpensive Cu(OAc) 2·H2O and phenylhydrazine. Georg Thieme Verlag Stuttgart . New York.
- Komori, Takashi,Satoh, Nobuhiro,Yokoshima, Satoshi,Fukuyama, Tohru
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- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
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We report herein that amides are excellent N-sources in the NHC-Pd(II)-Im complex 1 catalyzed amination of aryl chlorides. In the presence of KO tBu, various aryl chlorides and amides can react smoothly to give the corresponding aminated products in moderate to almost quantitative yields at room temperature within 6 h.
- Chen, Wen-Xin,Shao, Li-Xiong
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- Nickel Dual Photoredox Catalysis for the Synthesis of Aryl Amines
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In this work, a new dual photoredox nickel catalysis system has been utilized for the synthesize of aryl amines. Previously, our group has shown that a nickel catalyst in conjunction with a photosensitizer and a sacrificial electron donor can cross-couple C-C bonds via photoredox-assisted reductive coupling. Here we have built upon that system to develop a redox-neutral cross-coupling system for the formation of C-N bonds. The catalytic system is composed of just a nickel cross-coupling catalyst, a Ru photocatalyst, and base and is capable of coupling amines with aryl halides in good to excellent yields. Furthermore, it was found that these reactions are functional under ambient conditions with catalyst loadings of 1 mol %. Spectroscopic studies provide support that this amination mechanism proceeds via a nitrogen-based radical intermediate. This N-radical mechanism offers direct synthetic access to di- and triaryl amines from nickel photocatalysis.
- Key, Ryan J.,Vannucci, Aaron K.
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- Modified graphene supported Ag-Cu NPs with enhanced bimetallic synergistic effect in oxidation and Chan-Lam coupling reactions
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Herein, well dispersed Ag-Cu NPs supported on modified graphene have been synthesized via a facile and rapid approach using sodium borohydride as a reducing agent under ambient conditions. Dicyandiamide is selected as an effective nitrogen source with TiO2 as an inorganic material to form two kinds of supports, labelled as TiO2-NGO and NTiO2-GO. Initially, the surface area analysis of these two support materials was carried out which indicated that N-doping of GO followed by anchoring with TiO2 has produced support material of larger surface area. Using both types of supports, ten nano-metal catalysts based on Ag and Cu were synthesized. Benefiting from the bimetallic synergistic effect and larger specific surface area of TiO2-NGO, Cu?Ag-TiO2-NGO is found to be a highly active and reusable catalyst out of other synthesized catalysts. It exhibits excellent catalytic activity for oxidation of alcohols and hydrocarbons as well as Chan-Lam coupling reactions. The nanocatalyst is intensively characterized by BET, SEM, HR-TEM, ICP-AES, EDX, CHN, FT-IR, TGA, XRD and XPS. This journal is
- Choudhary, Anu,Gupta, Monika,Kaur, Manpreet,Paul, Satya,Sharma, Chandan,Sharma, Nitika
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- Amination of aryl chlorides in water catalyzed by cyclopalladated ferrocenylimine complexes with commercially available monophosphinobiaryl ligands
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The easily accessible, air- and moisture-stable cyclopalladated ferrocenylimine complex 3 was found to be a highly active one-component precatalyst for the amination of aryl chlorides in water in the presence of inexpensive KOH and t-BuOH as a base and an additive, respectively.
- Xu, Chen,Gong, Jun-Fang,Wu, Yang-Jie
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- A quinoxaline-based porous organic polymer containing copper nanoparticles CuNPs@Q-POP as a robust nanocatalyst toward C-N coupling reaction
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A novel porous organic polymer (denoted by Q-POP) was successfully fabricated by free-radical copolymerization of allyl-substituted 2,3-di(2-hydroxyphenyl)1,2-dihydroquinoxaline, and divinylbenzene under solvothermal conditions and used as a new platform for immobilization of copper nanoparticles. The CuNPs@Q-POP nanocatalyst was prepared via incorporating of Cu(NO3)2 into the polymeric network, followed by the reduction of Cu2+ ion with hydrazine hydrate. The obtained materials were characterized through FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and the single-crystal X-ray crystallography. The results displayed that Q-POP and CuNPs@Q-POP possessed high surface area, hierarchical porosity, and excellent thermal and chemical stability. The as-synthesized catalyst was utilized for the Ullmann C-N coupling reaction of aromatic amines and different aryl halides to prepare various diarylamine derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C-N coupling reaction with aromatic amines to produce diaryl amines in good to excellent yields (50-98%), and it turned out that aryl iodides have the best results. Besides, due to the strong interactions between CuNPs, N, and O-atoms of quinoxaline moiety existing in the polymeric framework, the copper leaching from the support was not observed. Furthermore, the catalyst was recycled and reused for five consecutive runs without significant activity loss.
- Gorginpour, Forough,Zali-Boeini, Hassan,Rudbari, Hadi Amiri
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- Molecular Adsorbates Switch on Heterogeneous Catalysis: Induction of Reactivity by N-Heterocyclic Carbenes
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We report the N-heterocyclic carbene (NHC)-induced activation of an otherwise unreactive Pd/Al2O3 catalyst. Surface analysis techniques demonstrate the NHC being coordinated to the palladium particles and affecting their electronic properties. Ab initio calculations provide further insight into the electronic effect of the coordination with the NHC injecting electron density into the metal nanocluster thus lowering the barrier for bromobenzene activation. By this NHC modification, the catalyst could be successfully applied in the Buchwald-Hartwig amination of aryl chlorides, bromides, and iodides. Various heterogeneity tests could additionally show that the reaction proceeds via a heterogeneous active species.
- Ernst, Johannes B.,Schwermann, Christian,Yokota, Gen-Ichi,Tada, Mizuki,Muratsugu, Satoshi,Doltsinis, Nikos L.,Glorius, Frank
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- Evaluation of aromatic amination catalyzed by palladium on carbon: A practical synthesis of triarylamines
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A heterogeneous palladium on carbon (Pd/C)-catalyzed coupling between amines and aromatic halides including aromatic chlorides has been achieved using sodium tert-butoxide (NaO-t-Bu) and 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a ligand in cyclopentyl methyl ether (CPME). The use of potassium tert-butoxide (KO-t-Bu) in place of NaO-t-Bu brought about the benzyne-mediated aromatic amination even without Pd/C and dppf, giving a mixture of regioisomers when 4-substituted bromobenzenes were employed as the substrate. The combination of Pd/C, dppf, NaO-t-Bu could be utilized for the syntheses of a broad range of triarylamines by replacing CPME with mesitylene which can provide a higher reaction temperature. The Pd/C could be quantitatively recovered and reused until at least the fourth cycle without any loss in catalytic activity. The quite low leaching of palladium (1.1%) was demonstrated by an inductively coupled plasma-atomic emission spectrometric analysis.
- Monguchi, Yasunari,Kitamoto, Katsunori,Ikawa, Takashi,Maegawa, Tomohiro,Sajiki, Hironao
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- Scope and limitations of Pd2(dba)3/P(i-BuNCH 2CH2)3N-catalyzed Buchwald-Hartwig amination reactions of aryl chlorides
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Proazaphosphatrane ligands in combination with Pd2(dba) 3 generate highly active catalysts for Buchwald-Hartwig amination of aryl chlorides. In particular, commercially available P(i-BuNCH 2-CH2)3N is a highly general and efficient ligand, allowing the coupling of an electronically diverse set of aryl chlorides, including chloropyridines, with a wide variety of amines using 1 mol % of Pd at 100 °C. Either a 1:1 or 2:1 ratio of ligand to Pd was found to be effective. This catalyst system performs exceptionally well for sterically hindered substrates, even with only 0.25 mol % of Pd. It is shown that NaOH can also be used as the base (instead of NaO-t-Bu) allowing functionalized substrates to participate in these reactions.
- Urgaonkar, Sameer,Verkade, John G.
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- Visible-Light- And PPh3-Mediated Direct C-N Coupling of Nitroarenes and Boronic Acids at Ambient Temperature
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We present here a metal-free, visible-light- and triphenylphosphine-mediated intermolecular, reductive amination between nitroarenes and boronic acids at ambient temperature without any photocatalyst. Mechanistically, a slow reduction of nitroarenes to a nitroso and, finally, a nitrene intermediate occurs that leads to the amination product with concomitant 1,2-aryl/-alkyl migration from a boronate complex. A wide range of nitroarenes underwent C-N coupling with aryl-/alkylboronic acids providing high yields.
- Manna, Kartic,Ganguly, Tanusree,Baitalik, Sujoy,Jana, Ranjan
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supporting information
p. 8634 - 8639
(2021/11/01)
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- Preparation method 3- methoxyl diphenylamine (by machine translation)
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3 -methoxydiphenylamine, is obtained, by adding PEG - 800,methoxybenzonitrobenzene 140 °C to a high-pressure reaction kettle, and heating to 2h, after heating to, and heating the methanol, to react, with methanol to obtain, metoonitrobenzene. 3 - reaction liquid distilled dry solvent; is added to the high-pressure reaction kettle. 3 - and then reacted at room temperature, and stirred for, hours under reduced pressure . reaction solution is evaporated and distilled off under reduced pressure 90 °C, by a reaction solution distilled 10h from, a reaction, solution distilled, from a reaction, solution distilled from, a 3 - reaction solution evaporated; in a reaction solution of, a reaction, liquid distilled from, a reaction solution of a, reaction liquid distilled from a reaction, solution distilled from a reaction solution distilled from a reaction solution of a reaction solution. (by machine translation)
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Paragraph 0008
(2020/04/17)
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- PROSTACYCLIN RECEPTOR AGONIST
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A compound represented by formula (I) or an isomer or a pharmaceutically acceptable salt thereof. The present invention also relates to an application of the same in preparing a drug for treating a disease related to a PGI2 receptor.
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Paragraph 0088-0090; 0120-0122
(2020/12/22)
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- Reductive Molybdenum-Catalyzed Direct Amination of Boronic Acids with Nitro Compounds
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The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C?N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. Moreover, this general and step-economical synthesis of aromatic secondary amines showcases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.
- Suárez-Pantiga, Samuel,Hernández-Ruiz, Raquel,Virumbrales, Cintia,Pedrosa, María R.,Sanz, Roberto
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supporting information
p. 2129 - 2133
(2019/01/25)
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- Copper-catalyzed, ceric ammonium nitrate mediated N-arylation of amines
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Cu-Catalyzed, ligand- and base-free cross-coupling of aryl boronic acids with primary and secondary amines has been reported. This ‘Chan-Evans-Lam' reaction has revealed that at room temperature, with a catalytic amount of copper(ii) acetate and ceric ammonium nitrate (CAN) as an oxidant, N-arylation can result in an effective C-N bond formation. This air stable, practical, robust protocol enables tolerance towards a variety of functional groups on both boronic acid and amine partners.
- Gonela, Uma Maheshwar,Ablordeppey, Seth Y.
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supporting information
p. 2861 - 2864
(2019/02/17)
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- Diamines as interparticle linkers for silica-titania supported PdCu bimetallic nanoparticles in Chan-Lam and Suzuki cross-coupling reactions
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A series of highly efficient amine functionalized SiO2-TiO2 supported bimetallic PdCu catalysts with varied metal composition have been synthesized. Ethane-1,2-diamine, butane-1,4-diamine and hexane-1,6-diamine were employed as interparticle linkers for amine functionalization of a SiO2-TiO2 support material so as to study the effect of pendant chain length on stabilization and immobilization of bimetallic nanoparticles. The shortest carbon chain length on the support provided the best results, which may be due to the trapping of metal nanoparticles more efficiently by the basic nitrogen sites. The catalytic activities of these materials were evaluated for C-N and C-C coupling reactions. The most active catalyst, Pd1Cu1@12DA-STS, was characterized by various techniques including SEM, HR-TEM, ICP-AES, XRD, FTIR, EDX, CHN analysis and TGA studies. Moreover, the synthesized catalyst was found to be recyclable for up to five runs without significant loss of activity.
- Jamwal, Babita,Kaur, Manpreet,Sharma, Harsha,Khajuria, Chhavi,Paul, Satya,Clark
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p. 4919 - 4928
(2019/03/26)
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- Allyl complexes for use in coupling reactions
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A complex of formula (1), wherein, M is palladium or nickel, R1 and R2 are independently organic groups having 1-20 carbon atoms, or R1 and R2 are linked to form a ring structure with the phosphorus atom, R3 is selected from the group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, and substituted and unsubstituted metallocenyl, R4 is an organic group having 1-20 carbon atoms, n is 0, 1, 2, 3, 4 or 5, X is an anionic ligand. A process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions is also provided.
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Page/Page column 21; 22; 25; 26; 31
(2019/01/12)
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- Copper immobilized at a covalent organic framework: An efficient and recyclable heterogeneous catalyst for the Chan-Lam coupling reaction of aryl boronic acids and amines
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A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been readily prepared from commercially available and inexpensive reagents and was employed as an effective support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active heterogeneous catalyst which can effectively promote the Chan-Lam coupling reaction of aryl boronic acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without any observable change in structure and catalytic activity.
- Han, Yi,Zhang, Mo,Zhang, Ya-Qing,Zhang, Zhan-Hui
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p. 4891 - 4900
(2018/11/21)
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- Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates
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A simple and efficient method for transition-metal-free N-arylation of various amines by triarylsulfonium triflates is described. Both aliphatic and aromatic amines were smoothly converted at 80 °C in the presence of tBuOK or KOH to give the corresponding mono N-arylated products in good to high yields. The molar ratios of the reactants and the choice of bases had a big effect on the reaction. When a large excess of [Ph3S][OTf] and tBuOK were employed for primary amines under the standard conditions, the bis(N-phenyl) products were predominantly formed. This method was also applicable to the synthesis of bioactive N-phenyl amino acid derivatives. The control experiments, the deuterium labelling study, and the presence of regioisomers of N-arylated products when using 4-substituted triarylsulfonium triflates suggested that the reaction might proceed through an aryne intermediate. The present protocol demonstrated that triarylsulfonium salts are versatile arylation reagents in the construction of CAr?N bonds.
- Tian, Ze-Yu,Ming, Xiao-Xia,Teng, Han-Bing,Hu, Yu-Tian,Zhang, Cheng-Pan
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p. 13744 - 13748
(2018/09/14)
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- Method for synthesizing 3-(methylthio) dibenzenamine by light/nickel concerted catalysis
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The invention discloses a method for synthesizing 3-(methylthio) dibenzenamine by light/nickel concerted catalysis. According to the method, cheap 3-(methylthio) benzenamine and halogeno benzene are used as raw materials, a light/nickel concerted catalysis strategy is used for constructing C-N bonds for the first time, and pyridazines drug key intermediate 3-(methylthio) dibenzenamine is synthesized. The method has the advantages that 1) the use amount of a photocatalyst is low, and is 0.01-0.02% of the molar weight of the halogeno benzene; 2) nickel salt is directly used as a metal catalyst such as nickel bromide, and an external ligand is not required; 3) reaction conditions are gentle, and can be effectively carried out at the temperature of 40-50 DEG C; and 4) the product can be directly obtained by reduced pressure distillation and is easily separated. By the remarkable advantages, the method has good industrial application prospect.
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Paragraph 0035; 0060-0061
(2018/09/11)
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- An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
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A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
- Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
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p. 3911 - 3920
(2018/09/29)
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- Method for synthesizing diarylamine by optical/nickel concerted catalysis
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The invention discloses a method for synthesizing diarylamine by optical/nickel concerted catalysis. According to the method, a ligand does not need to be added, and simple and cheap nickel salt is directly used as a metal catalyst to cooperate with a photosensitizer to catalyze arylamine and aryl bromide to generate cross-coupling. The method has the following advantages: (1) the use amount of BODIPY type organic photocatalyst is low, and the BODIPY type organic photocatalyst has a better catalysis effect in comparison with metal iridium and ruthenium photocatalysts reported in the literature; (2) the BODIPY type organic photocatalyst is easy for synthesis; (3) the use amount of nickel salt is few, and the ligand does not need to be added; and (4) the reaction conditions are mild, and theyield of most coupling products is higher than 90%. According to the method disclosed by the invention, high temperature and high pressure equipment is not needed, temperature change scope is small,experimental procedure is simple and easy to operate, and the method has a relatively high application value and industrial popularization potential.
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Paragraph 0046; 0047; 0048; 0049; 0144; 0145; 0146; 0147
(2018/09/08)
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- Synthesis and Photophysical Characterization of 2,3-Dihydroquinolin-4-imines: New Fluorophores with Color-Tailored Emission
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In this study, a series of variously substituted 2,3-dihydroquinolin-4-imines (DQIs) were synthesized from N-substituted propargylanilines by copper(I)-catalyzed annulation. The approach adopted in this study under mild, effective conditions exhibited broad substrate tolerance, particularly for functional groups substituted on anilines. Most of the DQI derivatives synthesized under optimal conditions were obtained in good isolated yields of 63–88 %. 2,3-Dihydroquinolinimine thus obtained was easily converted to important structures like 2,3-dihydroquinolone and tetrahydrobenzodiazepin-5-one, confirming the importance of this strategy in constructing various heterocycles. Surprisingly, 2,3-dihydroquinolinimines thus obtained exhibited bright fluorescence with quantum yields up to 66 %. The density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed for understanding the excited-state nature of DQI system. Accordingly, a tailored DQI derivative bearing methoxy group at C-6 position and acetoxy group at C-7 position was designed and synthesized to give emission at 559 nm with redshift compared to the 7-methoxy substituted DQI. A detailed study of DQI structures with their photophysical properties was performed with five control molecules and consequently demonstrated the uniqueness of the chemical structures of DQIs.
- Chou, Chih-Hung,Rajagopal, Basker,Liang, Chien-Fu,Chen, Kuan-Lin,Jin, Dun-Yuan,Chen, Hsing-Yin,Tu, Hsiu-Chung,Shen, Yu-Ying,Lin, Po-Chiao
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supporting information
p. 1112 - 1120
(2017/12/26)
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- A 2-methoxy phenothiazine synthesis method (by machine translation)
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The present invention provides a 2-methoxy phenothiazine synthesis method, comprising the following steps: step a, uniformly mixing the resorcinol and aniline, the heating and stirring add catalyst dehydration occurs under amination reaction produce intermediate I; step two, intermediate I plus solvent and alkali, under the heating conditions for the etherification reaction reagent instillment methylation intermediate II; step three, intermediate II plus solvent and sulfur, heating reflow conditions the initiation reaction of the iodine, the beginning of the generating ring reaction product 2-methoxy phenothiazine; step four, initial product 2-methoxy phenothiazine solvent recrystallization to obtain pure 2-methoxy phenothiazine. This invention adopts the single solvent, is not only conducive to separation and purification of the product, but also effectively reduce the cost of the solvent, also improve the industrial cleaning and safety of preparing reaction, the environmental pollution is reduced. At the same time separation, the recovered solvent can be recycled. (by machine translation)
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- Application of nanoparticle mediated N-arylation of amines for the synthesis of pharmaceutical entities using vit-E analogues as amphiphiles in water
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The first CuI-nanoparticle catalyzed inter and intramolecular N-arylation of amines using vitamin E analogues (TPGS) as amphipiles has been developed in water. Application of this transition metal-amphiphile C-N bond formation methodology is further extended for the synthesis of substituted indoles, bioactive natural product tryptanthrin and intermediates of pharmaceutical entities such as imatinib, nilotinib, selective D3 agonist/antagonist ligands, and oxacarbazepine. This journal is
- Kumar, Atul,Bishnoi, Ajay Kumar
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p. 20516 - 20520
(2015/03/30)
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- A tuned bicyclic proazaphosphatrane for catalytically enhanced n-arylation reactions with aryl chlorides
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The N-arylation of various amines with aryl chlorides proceeded in good-to-excellent yields in the presence of P[N{(p-NMe2)C6H4CH2}CH2CH2]3N (1e, a new electron-rich proazaphosphatrane ligand) and small amounts of Pd2(dba)3 (dba = dibenzylideneacetone). This catalytic system was also very effective for the synthesis of carbazoles. An efficient palladium-catalyzed N-arylation reaction of amines under mild conditions with a tuned bicyclic proazaphosphatrane has been developed.
- Kim, So Han,Kim, Min,Verkade, John G.,Kim, Youngjo
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p. 1954 - 1960
(2015/03/18)
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- A catalyst system, copper/ N -methoxy-1 H -pyrrole-2-carboxamide, for the synthesis of phenothiazines in poly(ethylene glycol)
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A copper/N-methoxy-1H-pyrrole-2-carboxamide catalyst system has been established for the preparation of phenothiazines in good yields by two routes, starting from 2-iodoanilines and 2-bromobenzenethiol and from aryl ortho-dihalides and o-aminobenzenethiols, by conducting the reaction at 90 °C in poly(ethylene glycol)-100 (PEG-100). In addition, the catalyst system was useful for promoting direct arylation of various aryl amines, aliphatic amines, and aqueous ammonia. The simple experimental operation, low loading of catalyst system together with the use of green solvent, makes it attractive for the versatile syntheses of phenothiazines and various amines.
- Huang, Manna,Hou, Jianying,Yang, Ruiqiao,Zhang, Liting,Zhu, Xinhai,Wan, Yiqian
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p. 3356 - 3364
(2015/02/02)
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- Arylation with unsymmetrical diaryliodonium salts: A chemoselectivity study
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Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new "anti-ortho effect" has been identified in the arylation of malonates. Several "dummy groups" have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents. Copyright
- Malmgren, Joel,Santoro, Stefano,Jalalian, Nazli,Himo, Fahmi,Olofsson, Berit
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supporting information
p. 10334 - 10342
(2013/09/02)
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- Direct amination of phenols under metal-free conditions
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Herein, we disclose the metal-free synthesis of arylamines via the direct amination of phenols using aminating reagents. This reaction procedure uses easy accessible aminating reagents and provides a versatile synthetic route to a broad range of arylamines with various functionalities in good to excellent yield. By using a two-step route of amination and oxidative coupling reaction, we synthesized three naturally occurring carbazole alkaloids: murrayafoline A, mukonine, and clausenine from two commercially available phenols. Georg Thieme Verlag Stuttgart · New York.
- Yu, Jianzhong,Wang, Yongtao,Zhang, Peizhi,Wu, Jun
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supporting information
p. 1448 - 1454
(2013/07/26)
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- Metal-free synthesis of secondary arylamines: An aliphatic-to-aromatic transformation
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An efficient method for the N-arylation of primary and some secondary amines using 2-halocyclohex-2-enones in an aliphatic-to-aromatic transformation in the presence of a substoichiometric amount of pTsOH has been developed. A series of arylamines have been synthesized from 2-halocyclohex-2-enones by in situ enamine formation followed by aromatization under environmentally friendly conditions using pTsOH. This metal-free, practical, relatively inexpensive protocol is of value in organic synthesis for industrial and academic applications. Copyright
- Barros, M. Teresa,Dey, Suvendu S.,Maycock, Christopher D.
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supporting information
p. 742 - 747
(2013/03/13)
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- A recyclable Cu-catalyzed C-N coupling reaction in water and its application to synthesis of imidazo[1,2-a]quinoxaline
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Polystyrene-supported pyrrole-2-carbohydrazide (PSP) was synthesized and combined with CuI to make up a recyclable heterogeneous catalytic system for Ullmann-type C-N coupling reaction in water. In which, a variety of functionalized aryl halides animated efficiently with anilines, benzylamine, aliphatic amines, and imidazole. its preliminary application resulted in a more practical synthesis of imidazo[1,2-a]quinoxaline.
- Huang, Liye,Yu, Ruina,Zhu, Xinhai,Wan, Yiqian
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supporting information
p. 8974 - 8977
(2013/09/23)
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- Pd-catalyzed synthesis of aryl amines via oxidative aromatization of cyclic ketones and amines with molecular oxygen
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Pd-catalyzed intermolecular aerobic dehydrogenative aromatizations have been developed for the arylation of amines with nonaromatic ketones. Under optimized reaction conditions, primary and secondary amines are selectively arylated in good yields with cyclohexanones and 2-cyclohexen-1-ones in the presence of a Pd-catalyst under an atmosphere of molecular oxygen.
- Girard, Simon A.,Knauber, Thomas,Zhou, Feng,Simon, Marc-Olivier,Li, Chao-Jun,Hu, Xiong,Deng, Guo-Jun
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supporting information
p. 5606 - 5609,4
(2012/12/12)
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- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
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We report herein that amides are excellent N-sources in the NHC-Pd(II)-Im complex 1 catalyzed amination of aryl chlorides. In the presence of KO tBu, various aryl chlorides and amides can react smoothly to give the corresponding aminated products in moderate to almost quantitative yields at room temperature within 6 h.
- Chen, Wen-Xin,Shao, Li-Xiong
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p. 9236 - 9239
(2013/01/15)
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- Well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides
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We report herein a well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides. Under the optimal reaction conditions, a variety of primary amines can be coupled with aryl chlorides to give the amination products in good to high yields within 4 h. It is worthy of noting here that the NHC-Pd(II)-Im complex showed especially high catalytic activity toward challenging sterically hindered substrates including both of aryl amines and aryl chlorides. In addition, alkyl amines were also proved to be suitable reaction partners to give the corresponding amination products in good to high yields.
- Zhu, Lei,Ye, Yue-Mei,Shao, Li-Xiong
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experimental part
p. 2414 - 2420
(2012/04/10)
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- Palladium- and nickel-catalyzed aminations of aryl imidazolylsulfonates and sulfamates
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A nickel complex derived from dppf, along with NaOt-Bu as the base, allowed for challenging aminations of aryl sulfamates. An improved functional group tolerance is observed in novel palladium-catalyzed aminations of imidazolylsulfonates with rac-BINAP as the ligand.
- Ackermann, Lutz,Sandmann, Rene,Song, Weifeng
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supporting information; experimental part
p. 1784 - 1786
(2011/06/10)
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- Air-stable Pd(R-allyl)LCl (L= Q-Phos, P(t-Bu)3, etc.) Systems for C-C/N Couplings: Insight into the Structure - Activity Relationship and Catalyst Activation Pathway
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A series of Pd(R-allyl)LCl complexes [R = H, 1-Me, 1-Ph, 1-gem-Me 2, 2-Me; L = Q-Phos, P(t-Bu)3, P(t-Bu)2-(p- NMe2C6H4), P(t-Bu)2Np] have been synthesized and evaluated in the Buchwald - Hartwig aminations in detail, in addition to the preliminary studies on Suzuki coupling and α-arylation reactions. Pd(crotyl)Q-PhosCl (9) was found to be a superior catalyst to the other Q-Phos-based catalysts, and the reported in situ systems, in model coupling reactions involving 4-bromoanisole substrate with either N-methylaniline or 4-tertbutylbenzeneboronic acid. Precatalyst 9 also performed better (Figure presented) than the catalysts bearing P(t-Bu)2(p- NMe2C6H4) ligand; however, it is comparable to the new crotyl catalysts bearing P(t-Bu)3 or P(t-Bu)2Np ligands. In α-arylation of a biologically important model substrate, 1-tetralone, Pd(allyl)P(t-Bu)2(p-NMe2C6H 4)Cl (15) was found to be the best catalyst. The reason for the relatively higher activity of the crotyl complexes in comparison to the allyl derivatives in C-N bond formation reactions was investigated using X-ray crystallography in conjunction with NMR spectroscopic studies.
- Seechurn, Carin C.C. Johansson,Parisel, Sebastien L.,Colacot, Thomas J.
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experimental part
p. 7918 - 7932
(2011/11/30)
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- Kinesin spindle protein (KSP) inhibitors with 2,3-fused indole scaffolds
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Mitotic kinesin spindle protein (KSP) is involved in the assembly of the bipolar spindle during cell division. On the basis of a common 2,3-fused indole substructure within the complex frameworks of terpendole E and other KSP inhibitors, the carbazoles with a bulky alkyl group were identified as a novel KSP inhibitory scaffold. Additionally, among several naturally occurring cell growth inhibitors with 2,3-fused indole structures,β-carboline alkaloids, harman and harmine, showed moderate inhibition of KSP.
- Oishi, Shinya,Watanabe, Toshiaki,Sawada, Jun-Ichi,Asai, Akira,Ohno, Hiroaki,Fujii, Nobutaka
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experimental part
p. 5054 - 5058
(2010/09/05)
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- Palladium-catalyzed direct synthesis of carbazoles via one-pot N-arylation and oxidative biaryl coupling: Synthesis and mechanistic study
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(Chemical Equation Presented) An efficient catalytic system has been developed for the synthesis of carbazoles by one-pot N-arylation and oxidative biaryl coupling. A significant substituent effect of the diarylamine intermediate on oxidative coupling was observed. Mechanistic studies of oxidative coupling, including trapping of reaction intermediates and kinetic isotope effect experiments, are also presented.
- Watanabe, Toshiaki,Oishi, Shinya,Fujii, Nobutaka,Ohno, Hiroaki
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experimental part
p. 4720 - 4726
(2009/10/02)
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- (t-Bu)2PN=P(i-BuNCH2CH2)3N: New efficient ligand for palladium-catalyzed C-N couplings of aryl and heteroaryl bromides and chlorides and for vinyl bromides at room temperature
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(Chemical Equation Presented) By employing Pd(OAc)2, Cs 2CO3, or NaOH, and the new ligand (t-Bu) 2PN=P(i-BuNCH2CH2)3N (3a), an electronically diverse array of aryl bromides and chlorides possessing base-sensitive substituents (nitro, ester, and keto) provide coupling products with bulky aryl amines in good to excellent yields. Aryl halides possessing other functional groups including cyano, amino, trifluoromethyl, and phenol, coupled with equal ease, producing highly functionalized amines in good to excellent yields. Moreover, an aryl chloro group can be preserved in the presence of a bromo substituent under our reaction conditions. BOC-protected amines also participated efficiently. Heterocyclic bromides and chlorides underwent clean couplings with amines in excellent yields. An important strength of our protocol is the use of lower palladium loadings than those reported earlier, without compromising yields. The air-stable palladium complex (η3-cinnamyl)PdCl·(3a) (5) was also employed successfully in C-N coupling reactions while the crotyl analogue was less efficacious. The 3a/Pd(OAc)2 catalyst system promotes, for the first time, efficient coupling of vinyl bromides with a variety of amines to produce imines and enamines at room temperature.
- Reddy, Ch. Venkat,Kingston, Jesudoss V.,Verkade, John G.
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p. 3047 - 3062
(2008/09/19)
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- A mild inter- and intramolecular amination of aryl halides with a combination of CuI and CsOAc
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A unique combination of CuI and CsOAc was found to catalyze aryl amination under mild conditions. The reaction takes place at room temperature or at 90 °C with broad functional group compatibility. The intramolecular reaction was able to form five-, six-, and seven-membered rings with various protecting groups on the nitrogen atom. The scope of the intermolecular amination, as well as its applications to unsymmetrical N,N′-dialkylated phenylenediamines, was investigated.
- Kubo, Tetsuji,Katoh, Chiharu,Yamada, Ken,Okano, Kentaro,Tokuyama, Hidetoshi,Fukuyama, Tohru
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experimental part
p. 11230 - 11236
(2009/04/11)
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- Anionic N-fries rearrangement of N-carbamoyl diarylamines to anthranilamides. Methodology and application to acridone and pyranoacridone alkaloids
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A general alkyllithium/LDA-mediated rearrangement of N-carbamoyl diarylamines 7a-g into the anthranilamides 8a-g and 9a-g (Table 1) is presented and applied to a regioselective efficient construction of acridone (17) and pyranoacridone (18) alkaloids (Scheme 4).
- MacNeil, Stephen L.,Wilson, Brian J.,Snieckus, Victor
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p. 1133 - 1136
(2007/10/03)
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- Facile N-arylation of amines and sulfonamides and O-arylation of phenols and arenecarboxylic acids
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An efficient, transition-metal-free procedure for the N-arylation of amines, sulfonamides, and carbamates and O-arylation of phenols and carboxylic acids has been achieved by allowing these substrates to react with a variety of o-silylaryl inflates in the presence of CsF. Good to excellent yields of arylated products are obtained under very mild reaction conditions. This chemistry readily tolerates a variety of functional groups.
- Liu, Zhijian,Larock, Richard C.
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p. 3198 - 3209
(2007/10/03)
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- P(i-BuNCH2CH2)3N: An effective ligand in the palladium-catalyzed amination of aryl bromides and iodides
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It is shown that the bicyclic triaminophosphine P(i-BuNCH2CH2)3N serves as an effective ligand for the palladium-catalyzed amination of a wide array of aryl bromides and iodides. Other bicyclic or acyclic triaminophosphines, even those of similar basicity and/or bulk, were inferior.
- Urgaonkar, Sameer,Nagarajan,Verkade
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p. 452 - 459
(2007/10/03)
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- P[N(i-Bu)CH2CH2]3N: A versatile ligand for the Pd-catalyzed amination of aryl chlorides
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(Matrix presented) Palladium-catalyzed amination reactions of aryl chlorides with amines proceeded in the presence of the bicyclic triaminophosphine P[N(i-Bu)CH2CH2]3N to afford the corresponding arylamines in good to excellent yields. Electron-poor, electron-neutral, and electron-rich aryl chlorides all participated with equal ease.
- Urgaonkar, Sameer,Nagarajan,Verkade, John G.
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p. 815 - 818
(2007/10/03)
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