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Reductive C?N Coupling of Nitroarenes: Heterogenization of MoO3 Catalyst by Confinement in Silica
The construction of C?N bonds with nitroaromatics and boronic acids using highly efficient and recyclable catalysts remains a challenge. In this study, nanoporous MoO3 confined in silica serves as an efficient heterogeneous catalyst for C?N cross-coupling of nitroaromatics with aryl or alkyl boronic acids to deliver N-arylamines and with desirable multiple reusability. Experimental results suggest that silica not only heterogenizes the Mo species in the confined mesoporous microenvironment but also significantly reduces the reaction induction period and regulates the chemical efficiency of the targeted product. The well-shaped MoO3@m?SiO2 catalyst exhibits improved catalytic performance both in yield and turnover number, in contrast with homogeneous Mo catalysts, commercial Pd/C, or MoO3 nanoparticles. This approach offers a new avenue for the heterogeneous catalytic synthesis of valuable bioactive molecules.
Yang, Fu,Dong, Xuexue,Shen, Yang,Liu, Mengting,Zhou, Hu,Wang, Xuyu,Li, Lulu,Yuan, Aihua,Song, Heng
p. 3413 - 3421
(2021/07/31)

Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids
The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of nitroarenes with arylboronic acids was developed. A variety of diarylamines were synthesized without the need for transition-metal catalysts. The reaction could be scaled up efficiently in a flow cell and several derivatization reactions were carried out smoothly. Cyclic voltammetry experiments and mechanism studies showed that acetonitrile, formic acid, and triethyl phosphite all played a role in promoting this reductive arylation transformation.
Wang, Dan,Wan, Zhaohua,Zhang, Heng,Alhumade, Hesham,Yi, Hong,Lei, Aiwen
p. 5399 - 5404
(2021/10/20)

Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles
A new N-heterocyclic carbene (NHC) precursor of imidazolium chloride and its corresponding Cu(I)–NHC complex 1 was synthesized. The complex 1 was found to be a highly effective catalyst for Chan-Evans-Lam coupling of arylboronic acid with amines and azoles (including imidazole, pyrazole and triazole), without addition of base at room temperature. Various substituents on three substrates can be tolerated, giving the desired coupling products in good to excellent yields (62–94%). The method is practical and offers an alternative to the corresponding copper-catalyzed Chan-Evans-Lam process for the construction of C–N bonds.
Zhang, Maoyuan,Xu, Zengbing,Shi, Dabin
(2020/12/25)

Mediator-Enabled Electrocatalysis with Ligandless Copper for Anaerobic Chan-Lam Coupling Reactions
Simple copper salts serve as catalysts to effect C-X bond-forming reactions in some of the most utilized transformations in synthesis, including the oxidative coupling of aryl boronic acids and amines. However, these Chan-Lam coupling reactions have historically relied on chemical oxidants that limit their applicability beyond small-scale synthesis. Despite the success of replacing strong chemical oxidants with electrochemistry for a variety of metal-catalyzed processes, electrooxidative reactions with ligandless copper catalysts are plagued by slow electron-transfer kinetics, irreversible copper plating, and competitive substrate oxidation. Herein, we report the implementation of substoichiometric quantities of redox mediators to address limitations to Cu-catalyzed electrosynthesis. Mechanistic studies reveal that mediators serve multiple roles by (i) rapidly oxidizing low-valent Cu intermediates, (ii) stripping Cu metal from the cathode to regenerate the catalyst and reveal the active Pt surface for proton reduction, and (iii) providing anodic overcharge protection to prevent substrate oxidation. This strategy is applied to Chan-Lam coupling of aryl-, heteroaryl-, and alkylamines with arylboronic acids in the absence of chemical oxidants. Couplings under these electrochemical conditions occur with higher yields and shorter reaction times than conventional reactions in air and provide complementary substrate reactivity.
Walker, Benjamin R.,Manabe, Shuhei,Brusoe, Andrew T.,Sevov, Christo S.
supporting information
p. 6257 - 6265
(2021/05/07)

Enolizable Ketones as Activators of Palladium(II) Precatalysts in Amine Arylation Reactions
Enolizable ketones have been identified as effective activators for palladium(II) precatalysts in the coupling of aryl bromides and aniline. N-arylation reactions catalyzed by [(DTBNpP)PdCl2]2 (DTBNpP = (bis(tert-butyl)neopentylphosphine) and PEPPSI-IPr precatalysts are activated by the addition of acetone, mesityl oxide, and 3-pentanone. 3-Pentanone was the most effective activator. Mechanistic studies show that acetone, 3-pentanone, and mesityl oxide reduce [(DTBNpP)PdCl2]2 in the presence of NaO-t-Bu to Pd0(DTBNpP)2
Hu, Huaiyuan,Gilliam, Ashley M.,Qu, Fengrui,Shaughnessy, Kevin H.
p. 4127 - 4135
(2020/05/05)

Aryl Amination Using Soluble Weak Base Enabled by a Water-Assisted Mechanism
The amination of aryl halides has become one of the most commonly practiced C-N bond-forming reactions in pharmaceutical and laboratory syntheses. The widespread use of strong or poorly soluble inorganic bases for amine activation nevertheless complicates the compatibility of this important reaction class with sensitive substrates as well as applications in flow and automated synthesis, to name a few. We report a palladium-catalyzed C-N coupling using Et3N as a weak, soluble base, which allows a broad substrate scope that includes bromo- and chloro(hetero)arenes, primary anilines, secondary amines, and amide type nucleophiles together with tolerance for a range of base-sensitive functional groups. Mechanistic data have established a unique pathway for these reactions in which water serves multiple beneficial roles. In particular, ionization of a neutral catalytic intermediate via halide displacement by H2O generates, after proton loss, a coordinatively unsaturated Pd-OH species that can bind amine substrate triggering intramolecular N-H heterolysis. This water-assisted pathway operates efficiently with even weak terminal bases, such as Et3N. The use of a simple, commercially available ligand, PAd3, is key to this water-assisted mechanism by promoting coordinative unsaturation in catalytic intermediates responsible for the heterolytic activation of strong element-hydrogen bonds, which enables broad compatibility of carbon-heteroatom cross-coupling reactions with sensitive substrates and functionality.
Lau, Sii Hong,Yu, Peng,Chen, Liye,Madsen-Duggan, Christina B.,Williams, Michael J.,Carrow, Brad P.
supporting information
p. 20030 - 20039
(2021/01/01)

Synthesis and characterization of new square planar heteroleptic cationic complexes [Ni(ii) β-oxodithioester-dppe]+; Their use as a catalyst for Chan-Lam coupling
Novel heteroleptic [Ni(ii) β-oxodithioester-dppe]+PF6- complexes (β-oxodithioester = methyl-3-hydroxy-3-benzyl-2-propenedithioate L1 1, methyl-3-hydroxy-3-(p-methoxyphenyl)-2-propenedithioate L2 2, methyl-3-hydroxy-3-(naphthyl)-2-propenedithioate L3 3, methyl-3-hydroxy-3-(p-chlorophenyl)-2-propenedithioate L4 4, methyl-3-hydroxy-3-(p-bromophenyl)-2-propenedithioate L5 5 and methyl-3-hydroxy-3-(p-cyanophenyl)-2-propenedithioate L6 6) have been synthesized and characterized by elemental (C, H, N) analysis, ESI-MS, IR, UV-visible, 1H, 13C{1H}, 31P{1H} and 19F{1H} NMR spectroscopy. The distorted square planar structures of the isomorphous cationic complexes 2, 3, 4 and 5 have been determined by X-ray crystallography. The catalytic activities of 1-6 were investigated for the Chan-Lam coupling reaction involving arylboronic acids and amines to afford N-arylated products in good to excellent yields under mild conditions with 1 mol% catalyst loading. This catalytic protocol offers significant functional group tolerance, and is endowed with a broad substrate scope. This journal is
Kumari, Kavita,Kumar, Saurabh,Singh, Krishna Nand,Drew, Michael G. B.,Singh, Nanhai
p. 12143 - 12153
(2020/07/30)

A new copper complex on graphene oxide: A heterogeneous catalyst for N-arylation and C-H activation
Graphene oxide supported Cu (II) ligand complex (GO?AP/L-Cu) has been synthesized and characterized by FT-IR, Raman, PXRD, UV–Visible, TGA, XPS, FESEM, TEM, EDAX, Elemental mapping, BET, CHNS and AAS analysis. The complex has been found to be efficient and reusable heterogeneous catalyst for the N-arylation and C-H activation reactions, both the catalytic reactions were found to be simple, cleaner and give high yields (~ 90%) of product. The catalyst can be easily filtered out from the reaction mixture and reused up to four times without significant loss of catalytic activity. The reported method is economical and novel in the sense that aqueous medium was used for both the reactions and for the stability of the catalyst. All isolated organic products were fully characterized on the basis of their physical and spectral data.
Mittal, Ayushi,Kumari, Shweta,Parmanand,Yadav, Deepak,Sharma, Sunil K.
(2019/12/15)

Modified graphene supported Ag-Cu NPs with enhanced bimetallic synergistic effect in oxidation and Chan-Lam coupling reactions
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
p. 30048 - 30061
(2020/10/06)

PROSTACYCLIN RECEPTOR AGONIST
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; 0101-0103

(2020/12/22)

Synthesis of unsymmetrically substituted triarylaminesviaacceptorless dehydrogenative aromatization using a Pd/C andp-toluenesulfonic acid hybrid relay catalyst
An efficient and convenient procedure for synthesizing triarylamines based on a dehydrogenative aromatization strategy has been developed. A hybrid relay catalyst comprising carbon-supported Pd (Pd/C) andp-toluenesulfonic acid (TsOH) was found to be effective for synthesizing a variety of triarylamines bearing different aryl groups starting from arylamines (diarylamines or anilines), using cyclohexanones as the arylation sources under acceptorless conditions with the release of gaseous H2. The proposed reaction comprises the following relay steps: condensation of arylamines and cyclohexanones to produce imines or enamines, dehydrogenative aromatization of the imines or enamines over Pd nanoparticles (NPs), and elimination of H2from the Pd NPs. In this study, an interesting finding was obtained indicating that TsOH may promote the dehydrogenation.
Jin, Xiongjie,Koizumi, Yu,Mizuno, Noritaka,Nozaki, Kyoko,Takayama, Satoshi,Yamaguchi, Kazuya,Yatabe, Takafumi
p. 4074 - 4084
(2020/05/25)

PEt3-mediated deoxygenative C–N coupling of nitroarenes and boronic acids
A method for the preparation of aryl- and heteroarylamine products by triethylphosphine-mediated deoxygenative coupling of nitroarenes and boronic acids is reported. This method provides access to an array of functionalized (hetero)arylamine products from readily available starting materials under the action of an inexpensive commercial reagent. The developed triethylphosphine-mediated transformation highlights the capability of organophosphorus compounds to carry out this useful deoxygenative transformation without the necessity of any transition metal additives.
Nykaza, Trevor V.,Yang, Junyu,Radosevich, Alexander T.
supporting information
p. 3248 - 3252
(2019/04/25)

“On Water” promoted N-arylation reactions using Cu (0)/myo-inositol catalytic system
Myo-inositol is originally applied as a cardiovascular medicine in clinic, which can be multi-ton manufactured via extraction from the byproducts in agricultural product processing such as defatted rice bran and corn-soaking water. Herein, the application of myo-inositol (MI) as a novel versatile tridentate O-donor ligand has been first described for promoting Cu-catalyzed amination reaction in aqueous medium.
Zhou, Qifan,Du, Fangyu,Chen, Yuanguang,Fu, Yang,Chen, Guoliang
supporting information
p. 1938 - 1941
(2019/06/24)

Copper(ii)-catalyzed c-n coupling of aryl halides and n-nucleophiles promoted by quebrachitol or diethylene glycol
Herein, we report the natural ligand quebrachitol (QCT) as a promoter for a Cu(II) catalyst, which is highly effective for N-Arylation of various amines and related aryl halides. A series of diarylamine derivatives were obtained in high yields by using diethylene glycol (DEG) as both ligand and solvent. The C-N coupling reactions proceed under mild conditions and exhibit good functional group tolerance.
Chen, Guoliang,Chen, Yuanguang,Du, Fangyu,Fu, Yang,Wu, Ying,Zhou, Qifan
supporting information
p. 2161 - 2168
(2019/11/25)

Ullmann-type: N-arylation of anilines with alkyl(aryl)sulfonium salts
A palladium/copper-cocatalyzed Ullmann-type N-arylation of anilines using alkyl(aryl)sulfonium triflates as arylation reagents has been accomplished. The reaction enabled Caryl-S bond cleavage over Calkyl-S bond breakage of alkyl(aryl)sulfoniums by Pd(P(tBu)3)2/CuI and gave the corresponding N-arylated products in good to high yields. It was also significant that the reactions of aniline with asymmetric butyl(mesityl)(aryl)sulfonium triflates showed excellent selectivity, in which the aryl groups other than the bulky and electron-rich mesityl moieties were transformed.
Tian, Ze-Yu,Zhang, Cheng-Pan
p. 11936 - 11939
(2019/10/11)

Reductive Molybdenum-Catalyzed Direct Amination of Boronic Acids with Nitro Compounds
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
supporting information
p. 2129 - 2133
(2019/01/25)

Nickel-catalyzed N-arylation of amines with arylboronic acids under open air
In this study, a well-defined, novel NHC-Ni complex was developed and used to catalyze the N-arylation of alkyl- and arylamines with arylboronic acids in a rare version of Chan-Lam coupling. Although the same coupling using copper catalysts has been widely studied, the nickel-catalyzed version is rare and normally requires 10–20 mol% catalyst loading. This novel NHC-Ni complex in combination with 4,4′-dimethyl-2,2′-bipyridine, however, proved to be an effective catalyst that lowered the required catalyst loading to only 2.0 mol%.
Ando, Shin,Hirota, Yurina,Matsunaga, Hirofumi,Ishizuka, Tadao
supporting information
p. 1277 - 1280
(2019/04/10)

Diamines as interparticle linkers for silica-titania supported PdCu bimetallic nanoparticles in Chan-Lam and Suzuki cross-coupling reactions
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
p. 4919 - 4928
(2019/03/26)

Electrochemically Enabled Chan-Lam Couplings of Aryl Boronic Acids and Anilines
The Chan-Lam reaction remains a highly utilized transformation for C-N bond formation. However, anilines remain problematic substrates due to their lower nucleophilicity. To address this problem, we developed an electrochemically mediated Chan-Lam coupling of aryl boronic acids and amines utilizing a dual copper anode/cathode system. The mild conditions identified have enabled the preparation of a wide range of functionalized biarylanilines in good yields and chemoselectivities.
Wexler, Ryan P.,Nuhant, Philippe,Senter, Timothy J.,Gale-Day, Zachary J.
supporting information
p. 4540 - 4543
(2019/06/27)

Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling
The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.
Roscales, Silvia,Csák?, Aurelio G.
supporting information
p. 1667 - 1671
(2018/03/23)

"on Water" Promoted Ullmann-Type C-N Bond-Forming Reactions: Application to Carbazole Alkaloids by Selective N-Arylation of Aminophenols
The Ullmann-type cross coupling of a variety of aromatic, aliphatic amines with aryl halides is reported using a CuI-based catalytic system in combination with an easily accessible prolinamide ligand in aqueous media. The method is mild and tolerant to air, moisture, and a wide range of functional groups, providing a novel way to access a variety of aminated products. Secondary amines like heteroaromatic amines and nucleobases have also been used, affording the corresponding coupling products in good to excellent yields. Moreover, this method has been employed for chemoselective C-N arylation of aminophenols and further utilized for the synthesis of carbazole natural products, avoiding the protection and deprotection steps.
Chakraborti, Gargi,Paladhi, Sushovan,Mandal, Tirtha,Dash, Jyotirmayee
p. 7347 - 7359
(2018/07/29)

8-exo-dig-Selective Cycloisomerization for the Synthesis of Dibenzo[b,e][1,4]diazocines Using Cationic AuI Catalysts
The cationic AuI-catalyzed intramolecular reaction of N-propargyl-2-anilinoanilines gave a diazocine skeleton via 8-exo-dig-selective cycloisomerization by the suppression of 6-endo-dig cycloisomerization. Both terminal and internal alkynes could be used according to the choice of ligand of the AuI complex, and various dibenzo[b,e][1,4]diazocines were obtained. Control experiments suggested that two nitrogen atoms in the tether of substrates were critical in this selective transformation.
Ito, Mamoru,Inoue, Daisuke,Takaki, Asahi,Kanyiva, Kyalo Stephen,Shibata, Takanori
supporting information
p. 4740 - 4747
(2018/09/14)

An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
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
p. 3911 - 3920
(2018/09/29)

Transition-metal-free synthesis of aromatic amines via the reaction of benzynes with isocyanates
An unexpected reaction between benzynes and isocyanates to generate aromatic amines has been developed under transition-metal-free conditions. The in situ prepared anions formed through cleavage of the N–C bond in isocyanates, reacted with aryne precursor
Seo, Jeong Hoon,Ko, Haye Min
supporting information
p. 671 - 674
(2018/01/19)

Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates
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
p. 13744 - 13748
(2018/09/14)

Palladium-catalyzed amination of aryl sulfoxides
Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C-S bond amination reactions. This amination accommodated a wider range of functional groups such as silyl, boryl, methylsulfanyl, and halogen moieties. Regioselective amination of unsymmetrical diaryl sulfoxides was also executed by means of steric bias.
Yoshida, Yuto,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
supporting information
p. 1134 - 1137
(2018/02/23)

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
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
p. 4891 - 4900
(2018/11/21)

Chan-Evans-Lam Couplings with Copper Iminoarylsulfonate Complexes: Scope and Mechanism
Copper(II) pyridyliminoarylsulfonate complexes with chloride or triflate counteranions were employed in Chan-Evans-Lam (CEL) couplings of N-nucleophiles and arylboronic acids. The complexes avoided typical side reactions in CEL couplings, and an excess of boronic acid was not required. Water was tolerated, and addition of neither base nor other additives was necessary. Primary amines, acyclic and cyclic secondary amines, anilines, aminophenol, imidazole, pyrazole, and phenyltetrazole can be quantitatively arylated at either 25 or 50 °C with 2.5 mol % of the catalyst. Reaction kinetics were investigated in detail. Kinetic and spectroscopic studies provide evidence for the formation of unproductive copper-substrate complexes. Formation of an aniline-phenylboronic acid adduct was responsible for the zero-order dependence of reaction rates on phenylboronic acid concentration. Kinetic evidence indicates that the order of reaction steps is transmetalation, nucleophile coordination, and oxidation. Couplings performed poorly with electron-deficient arylboronic acids, due to a slower Cu(II)/Cu(III) oxidation in the catalytic cycle. Photoredox catalysis partially resolved this problem, but addition of copper acetate as an external oxidant proved to be more efficient.
Hardouin Duparc, Valérie,Bano, Guillaume L.,Schaper, Frank
p. 7308 - 7325
(2018/07/05)

Cu(II) complex of phenylthiosemicarbazone: An in situ catalyst for formation of C-N bond between different N-based neucleophiles with arylboronic acids at room temperature
We have reported here a new synthetic protocol for the formation of C-N bond catalyzed by a thiosemicarbazone complex of copper. This in situ complex has been found to be very effective for Chan-Lam C-N cross-coupling reaction of anilines and various imidazoles at room temperature. Pyrazole and 4-bromoindole were also activated for C-N bond formation by using this protocol at room temperature. This catalytic system gave good-to-excellent yield using a mixture of DMF and water as solvent in a 1:1 proportion.
Gogoi, Nibedita,Borah, Geetika,Gogoi, Pradip K.
(2018/05/30)

Spectroscopic Studies of the Chan-Lam Amination: A Mechanism-Inspired Solution to Boronic Ester Reactivity
We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, including off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxidation/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I) → Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.
Vantourout, Julien C.,Miras, Haralampos N.,Isidro-Llobet, Albert,Sproules, Stephen,Watson, Allan J. B.
supporting information
p. 4769 - 4779
(2017/04/11)

Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald-Hartwig Amination in Air
To achieve efficient palladium-catalyzed cross-coupling reaction under mild reaction conditions with the flexible steric bulk strategy, a series of Pd-PEPPSI (PEPPSI: pyridine-enhanced precatalyst preparation, stabilization, and initiation) complexes C1-C6 were synthesized and characterized, in which unsymmetric flexible steric bulk was introduced on the N-aryl of ancenaphthyl skeleton. These well-defined palladium complexes were found to be excellent precatalysts for Buchwald-Hartwig amination of aryl chlorides with amines in air. The electronic effect of the Pd-PEPPSI complexes and the effect of ancillary pyridine ligands were evaluated, among which complex C3 exhibited the most efficiency. It was demonstrated that the cross-coupling products were obtained in excellent yields in the presence of 0.5-0.1 mol % palladium loading. A wide range of aryl- and heteroaryl chlorides as well as various amines were compatible. The oxidative addition of aryl chlorides is revealed to be the rate-determining step in the catalytic cycle. The catalytic activity can be enhanced by introducing electron-donating groups to the Pd-PEPPSI complexes. This type of Pd-PEPPSI precatalyst showed the most efficiency reported to date for the challenging C-N cross-coupling reactions requiring no anhydrous and inert atmosphere protections, suggesting flexible steric bulk as a promising catalyst design strategy.
Lan, Xiao-Bing,Li, Yinwu,Li, Yan-Fang,Shen, Dong-Sheng,Ke, Zhuofeng,Liu, Feng-Shou
p. 2914 - 2925
(2017/03/23)

From blue to green: Fine-tuning of photoluminescence and electrochemiluminescence in bifunctional organic dyes
We describe the synthesis, computational analysis, photophysics, electrochemistry and electrochemiluminescence (ECL) of a series of compounds formed of two triphenylamines linked by a fluorene or spirobifluorene bridge. The phenylamine moieties were modif
Rizzo, Fabio,Polo, Federico,Bottaro, Gregorio,Fantacci, Simona,Antonello, Sabrina,Armelao, Lidia,Quici, Silvio,Maran, Flavio
supporting information
p. 2060 - 2069
(2017/02/15)

Sulfonato-diketimine Copper(II) Complexes: Synthesis and Application as Catalysts in Chan-Evans-Lam Couplings
Copper complexes bearing a diketimino-sulfonate ligand, LCu(NO3)(NCMe), were prepared and proved to be stable to water for several hours in solution. Prolonged standing in the presence of water or strong bases led to desulfonation of the ligand. LCu(NO3) was inactive in the polymerization of lactide (in the presence of benzyl alcohol), but showed high activity for the Chan-Evans-Lam coupling of a variety of amines and anilines. Couplings do not require addition of base, ligand, or molecular sieves. Mechanistic investigations indicate a catalytic cycle involving dioxygen as the required oxidant, precoordination of boronic acid to the sulfonate group, and transmetalation occurring prior to reaction with the nucleophile.
Hardouin Duparc, Valérie,Schaper, Frank
p. 3053 - 3060
(2017/09/05)

Sulfonato-imino copper(II) complexes: Fast and general Chan-Evans-Lam coupling of amines and anilines
Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.
Hardouin Duparc,Schaper
supporting information
p. 12766 - 12770
(2017/10/11)

Versatile routes for synthesis of diarylamines through acceptorless dehydrogenative aromatization catalysis over supported gold-palladium bimetallic nanoparticles
Diarylamines are an important class of widely utilized chemicals, and development of diverse procedures for their synthesis is of great importance. Herein, we have successfully developed novel versatile catalytic procedures for the synthesis of diarylamines through acceptorless dehydrogenative aromatization. In the presence of a gold-palladium alloy nanoparticle catalyst (Au-Pd/TiO2), various symmetrically substituted diarylamines could be synthesized starting from cyclohexylamines. The observed catalysis of Au-Pd/TiO2 was heterogeneous in nature and Au-Pd/TiO2 could be reused several times without severe loss of catalytic performance. This transformation needs no oxidants and generates molecular hydrogen (three equivalents with respect to cyclohexylamines) and ammonia as the side products. These features highlight the environmentally benign nature of the present transformation. Furthermore, in the presence of Au-Pd/TiO2, various kinds of structurally diverse unsymmetrically substituted diarylamines could successfully be synthesized starting from various combinations of substrates such as (i) anilines and cyclohexanones, (ii) cyclohexylamines and cyclohexanones, and (iii) nitrobenzenes and cyclohexanols. The role of the catalyst and the reaction pathways were investigated in detail for the transformation of cyclohexylamines. The catalytic performance was strongly influenced by the nature of the catalyst. In the presence of a supported gold nanoparticle catalyst (Au/TiO2), the desired diarylamines were hardly produced. Although a supported palladium nanoparticle catalyst (Pd/TiO2) gave the desired diarylamines, the catalytic activity was inferior to that of Au-Pd/TiO2. Moreover, the activity of Au-Pd/TiO2 was superior to that of a physical mixture of Au/TiO2 and Pd/TiO2. The present Au-Pd/TiO2-catalyzed transformation of cyclohexylamines proceeds through complex pathways comprising amine dehydrogenation, imine disproportionation, and condensation reactions. The amine dehydrogenation and imine disproportionation reactions are effectively promoted by palladium (not by gold), and the intrinsic catalytic performance of palladium is significantly improved by alloying with gold. One possible explanation of the alloying effect is the formation of electron-poor palladium species that can effectively promote the β-H elimination step in the rate-limiting amine dehydrogenation.
Taniguchi, Kento,Jin, Xiongjie,Yamaguchi, Kazuya,Nozaki, Kyoko,Mizuno, Noritaka
p. 2131 - 2142
(2017/03/09)

Solvent-Free Buchwald-Hartwig (Hetero)arylation of Anilines, Diarylamines, and Dialkylamines Mediated by Expanded-Ring N-Heterocyclic Carbene Palladium Complexes
A highly efficient solvent-free protocol for the Buchwald-Hartwig (hetero)arylation of anilines, diarylamines, and dialkylamines mediated by the expanded-ring N-heterocyclic carbene palladium complex (THP-Dipp)Pd(cinn)Cl [THP-Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; cinn = cinnamyl, 3-phenylallyl] was developed. The catalytic protocol was efficient for the coupling of amines and (hetero)aryl chlorides and bromides bearing donor, acceptor, and bulky substituents.
Topchiy, Maxim A.,Dzhevakov, Pavel B.,Rubina, Margarita S.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
supporting information
p. 1908 - 1914
(2016/04/20)

SELECTIVE ANDROGEN RECEPTOR DEGRADER (SARD) LIGANDS AND METHODS OF USE THEREOF
This invention provides novel indole, indazole, benzimidazole, indoline, quinolone, isoquinoline, and carbazole selective androgen receptor degrader (SARD) compounds, pharmaceutical compositions and uses thereof in treating prostate cancer, advanced prostate cancer, castration resistant prostate cancer, androgenic alopecia or other hyper androgenic dermal diseases, Kennedy's disease, amyotrophic lateral sclerosis (ALS), and uterine fibroids, and to methods for reducing the levels of androgen receptor-full length (AR-FL) including pathogenic and/or resistance mutations, AR-splice variants (AR-SV), and pathogenic polyglutamine (polyQ) polymorphisms of AR in a subject.
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Paragraph 00435-00436

(2016/11/14)

SELECTIVE ANDROGEN RECEPTOR DEGRADER (SARD) LIGANDS AND METHODS OF USE THEREOF
This invention provides novel 3-amino propanamide selective androgen receptor degrader (SARD) compounds, pharmaceutical compositions and uses thereof in treating prostate cancer, advanced prostate cancer, castration resistant prostate cancer, androgenic alopecia or other hyperandrogenic dermal diseases, Kennedy's disease, amyotrophic lateral sclerosis (ALS), and uterine fibroids, and to methods for reducing the levels of androgen receptor-full length (AR-FL) including pathogenic or resistance mutations, AR-splice variants (AR-SV), and pathogenic polyglutamine (polyQ) polymorphisms of AR in a subject.
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Paragraph 00334; 00335; 00337

(2016/11/17)

Palladium-Catalyzed N-Arylation of Amines and Amides with Aryltrimethylgermanes
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
supporting information
p. 1945 - 1948
(2016/08/09)

Highly Chemoselective Iridium Photoredox and Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with Aryl Halides
A visible-light-promoted iridium photoredox and nickel dual-catalyzed cross-coupling procedure for the formation C?N bonds has been developed. With this method, various aryl amines were chemoselectively cross-coupled with electronically and sterically diverse aryl iodides and bromides to forge the corresponding C?N bonds, which are of high interest to the pharmaceutical industries. Aryl iodides were found to be a more efficient electrophilic coupling partner. The coupling reactions were carried out at room temperature without the rigorous exclusion of molecular oxygen, thus making this newly developed Ir-photoredox/Ni dual-catalyzed procedure very mild and operationally simple.
Oderinde, Martins S.,Jones, Natalie H.,Juneau, Antoine,Frenette, Mathieu,Aquila, Brian,Tentarelli, Sharon,Robbins, Daniel W.,Johannes, Jeffrey W.
supporting information
p. 13219 - 13223
(2016/10/30)

The solid copper-mediated C-N cross-coupling of phenylboronic acids under continuous flow conditions
We have developed two general methods for the C-N cross-coupling of phenylboronic acids with amines using solid copper flow reactors, in combination with an oxidant. We have developed one method for a C-N arylation reaction which employs a solid copper coil reactor, in combination with tert-butyl peroxybenzoate, to give products in moderate isolated yields. We have also developed a general method for the C-N cross coupling of phenylboronic acids using a column packed with solid copper powder, in combination with acetic acid and TEMPO, to give products in isolated yields in excess of 75+%. We have also applied our general copper powder method to generate a library of products which highlights the utility of solid copper flow reactors for C-N cross coupling reactions, generating 16 examples in good yields. Mechanistic implications and future directions are also discussed.
Bao, Jennifer,Tranmer, Geoffrey K.
p. 654 - 657
(2016/01/26)

A method for preparing aromatic amine derivative
The invention discloses a preparation method of a diarylamine ramification. The preparation method comprises the following steps: dissolving a phenylamine ramification, a phenylhydrazine ramification, a metal phthalocyanine ramification and a copper salt into a solvent, and reacting at -10 to 40 DEG C to obtain the diarylamine ramification. According to the preparation method, the phenylamine ramification and the phenylhydrazine ramification are taken as starting materials, so that raw materials are easy to obtain and plenty in variety; a product obtained by utilizing the method is plenty in type, can not only be directly used, but also be used for other further reactions; and no additive is required to be added. The preparation method disclosed by the invention has the advantages of short synthetic route, moderation in reaction condition, simple reaction operation and post-processing process, high yield and suitability for large-scale production.
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Paragraph 0136-0139

(2016/10/08)

CoPc/Cu(OAc)2-catalyzed N-arylation of amines with arylhydrazines leading to N-aryl amines
The N-arylation of amines with arylhydrazines has been developed, achieving the selective cross-coupling of aryl radicals with amines to form N-aryl amines. The reaction uses air as an oxidant, CoPc and Cu(OAc)2as catalysts. The reaction proceeds under mild conditions in air through a relay process, arylhydrazines are oxidized to aryldiazenes by CoPc, further oxidized to aryl radicals by air (O2), which are trapped by Cu(OAc)2–amine complex, followed by reduction–elimination reaction to form N-aryl amines. Arylamines and arylhydrazines give the highest yields, but N-aryl-N-alkylamines and N-alkylamines can be used as well.
Sun, Wang-Bin,Zhang, Pei-Zhi,Jiang, Tao,Li, Cheng-Kun,An, Li-Tao,Shoberu, Adedamola,Zou, Jian-Ping
p. 6477 - 6483
(2016/09/23)

Nickel(II) complex incorporating methylene bridged tetradentate dicarbene ligand as an efficient catalyst toward CC and CN bond formation reactions
For the evaluation of binding and catalytic nature of N-heterocyclic carbenes (NHCs) and their complexes, a new methylene bridged bis(aryloxy-NHC) ligand has been prepared. A novel air-stable Ni(II) complex bearing the new NHC ligand has been synthesized and characterized by elemental analysis, NMR (1H and 13C) as well as ESI-mass spectrometry. The molecular structure of the complex was identified by means of single crystal X-ray diffraction analysis which revealed that the Ni(II) complex possesses a square planar geometry with the ligand coordinating with bi-negative tetradentate C2O2 fashion and the complex showed efficient catalytic activity toward the Suzuki-Miyaura cross-coupling reaction between aryl halides and arylboronic acids under phosphine free conditions. The new complex also catalyzed the amination of aryl chlorides in the presence of KOtBu. Various aryl chlorides and amines can react smoothly to give the corresponding aminated products in moderate to high yields. Both secondary and primary amines are well tolerated under the optimal reaction conditions.
Nirmala, Muthukumaran,Prakash, Govindan,Ramachandran, Rangasamy,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz,Linert, Wolfgang
p. 56 - 67
(2015/02/05)

UV light-mediated difunctionalization of alkenes through aroyl radical addition/1,4-/1,2-Aryl shift cascade reactions
UV light-mediated difunctionalization of alkenes through an aroyl radical addition/1,4-/1,2-aryl shift has been described. The resulted aroyl radical from a photocleavage reaction added to acrylamide compounds followed by cyclization led to the formation of oxindoles, whereas the addition to cinnamic amides aroused a unique 1,4-aryl shift reaction. Furthermore, the difunctionalization of alkenes of prop-2-en-1-ols was also achieved through aroyl radical addition and a sequential 1,2-aryl shift cascade reaction.
Zheng, Lewei,Huang, Hongli,Yang, Chao,Xia, Wujiong
supporting information
p. 1034 - 1037
(2015/03/30)

N-(Pyridin-2-yl)benzamide: Efficient ligand for the nickel catalyzed Chan-Lam cross-coupling reaction
An efficient protocol for the Chan-Lam cross-coupling reactions of arylboronic acids with aryl or alkyl amines has been developed by employing simple N-(pyridin-2-yl)benzamide ligand with Ni(OAc)2·4H2O in the presence of TMG base. The reaction proceeded well with high yields by employing various N-nucleophiles at low catalytic loadings.
Keesara, Srinivas
p. 6685 - 6688
(2016/01/28)

Visible-Light-Mediated Chan-Lam Coupling Reactions of Aryl Boronic Acids and Aniline Derivatives
The copper(II)-catalyzed aerobic oxidative coupling reaction between aryl boronic acids and aniline derivatives was found to be improved significantly under visible-light-mediated photoredox catalysis. The substrate scope of this oxidative Chan-Lam reaction was thus expanded to include electron-deficient aryl boronic acids as viable starting materials. Two are better than one: The copper(II)-catalyzed aerobic oxidative coupling reaction between aryl boronic acids and anilines is significantly improved by the addition of visible-light-mediated photoredox catalysts. The substrate scope of this Chan-Lam reaction was thus expanded to include electron-deficient aryl boronic acids.
Yoo, Woo-Jin,Tsukamoto, Tatsuhiro,Kobayashi, Shu
supporting information
p. 6587 - 6590
(2015/06/02)

Synthesis and development of Chitosan anchored copper(II) Schiff base complexes as heterogeneous catalysts for N-arylation of amines
Abstract The Chitosan anchored Cu(II) Schiff base complexes (C1-C3) have been synthesized and characterized by FTIR, UV, FE-SEM, EDAX, TGA, AAS and elemental analysis. These complexes have been found to be efficient and recyclable heterogeneous catalysts for the Chan-Lam C-N coupling reaction of various aromatic/aliphatic amines with arylboronic acid under mild reaction conditions. These complexes can be easily filtered out from the reaction medium and reused up to five times without significant loss of catalytic activity.
Anuradha,Kumari, Shweta,Pathak, Devendra D.
supporting information
p. 4135 - 4142
(2015/08/03)

A catalyst system, copper/ N -methoxy-1 H -pyrrole-2-carboxamide, for the synthesis of phenothiazines in poly(ethylene glycol)
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
p. 3356 - 3364
(2015/02/02)

Ligand-free CuTC-catalyzed N-arylation of amides, anilines and 4-aminoantipyrine: Synthesis of N-arylacrylamides, 4-amido-N-phenylbenzamides and 4-amino(N-phenyl)antipyrenes
N-Arylation of amides and anilines with aryl iodides was efficiently catalyzed by copper thiophenecarboxylate under ligand-free conditions with good to excellent yields. A variety of substituted aryl iodides, amides, anilines and 4-aminoantipyrine were found to be applicable to the simple catalytic system. Furthermore, some practical, unique secondary amides, such as N-arylacrylamides and 4-amido-N-phenylbenzamides, and 4-amino(N-phenyl)antipyrenes, which are difficult to obtain by the classical methods, were prepared.
Quan, Zheng-Jun,Xia, Hai-Dong,Zhang, Zhang,Da, Yu-Xia,Wang, Xi-Cun
p. 81 - 85
(2014/02/14)