- Access to Dibenzofurans through Dimerization/Trimerization of Cyclohexanones Followed by Dehydroaromatization
-
A novel and efficient method for the synthesis of unsymmetrical substituted dibenzofurans has been developed, which can selectively produce disubstituted dibenzofurans and trisubstituted dibenzofurans products under metal-free conditions. This approach starts from cheap and available nonaromatic cyclohexanones, affording a simple and efficient access to unsymmetrical substituted dibenzofurans.
- Jiang, Pingyu,Chen, Shanping,Xia, Yi,Zhang, Qingqing,Deng, Guo-Jun
-
supporting information
p. 8076 - 8081
(2020/11/02)
-
- Cu-Catalyzed C-N Coupling with Sterically Hindered Partners
-
Copper, an earth-abundant metal, has reemerged as a viable alternative to the versatile Pd-catalyzed C-N coupling. Coupling sterically hindered reaction partners, however, remains challenging. Herein, we disclose the discovery and development of a pyrrole-ol ligand to facilitate the coupling of ortho-substituted aryl iodides with sterically hindered amines. The ligand was discovered through a library screening approach and highlights the value of mining heteroatom-rich pharmaceutical libraries for useful ligand motifs. Further evaluation revealed that this ligand is uniquely effective in these challenging transformations. The reaction enables the coupling of sterically hindered primary and secondary amines, anilines, and amides with broad functional group tolerance.
- Modak, Atanu,Nett, Alex J.,Swift, Elizabeth C.,Haibach, Michael C.,Chan, Vincent S.,Franczyk, Thaddeus S.,Shekhar, Shashank,Cook, Silas P.
-
p. 10495 - 10499
(2020/10/03)
-
- Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
-
A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by-product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4-coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron-deficient diaryliodonium salts.
- Stridfeldt, Elin,Lindstedt, Erik,Reitti, Marcus,Blid, Jan,Norrby, Per-Ola,Olofsson, Berit
-
p. 13249 - 13258
(2017/09/12)
-
- Green alternative solvents for the copper-catalysed arylation of phenols and amides
-
Investigation of the use of green organic solvents for the Cu-catalysed arylation of phenols and amides is reported. Alkyl acetates proved to be efficient solvents in the catalytic processes, and therefore excellent alternatives to the typical non-green solvents used for Cu-catalysed arylation reactions. Solvents such as isosorbide dimethyl ether (DMI) and diethyl carbonate also appear to be viable possibilities for the arylation of phenols. Finally, a novel copper catalysed acyl transfer process is reported.
- Sambiagio, Carlo,Munday, Rachel H.,John Blacker,Marsden, Stephen P.,McGowan, Patrick C.
-
p. 70025 - 70032
(2016/08/06)
-
- Palladium-Catalyzed Sequential Acylation/Cyanation of Aryl Iodides: A Regiospecific Synthesis of 2-Cyanoaryl Ketones
-
A palladium-catalyzed, norbornene-mediated acylation/cyanation reaction of iodobenzene was developed by the use of acyl chlorides as acylation reagents and cuprous cyanide. The reaction gave the 2-cyanoaryl ketones efficiently by using readily available starting materials. (Chemical Equation Presented).
- Pan, Shanfei,Wu, Feifei,Yu, Ruicheng,Chen, Wanzhi
-
p. 1558 - 1564
(2016/03/01)
-
- The coupling reactions of aryl halides and phenols catalyzed by palladium and MOP-type ligands
-
Palladium-catalyzed coupling reactions of aryl halides and phenols are described employing the bulky and electron-rich MOP-type ligands. When K3PO4 was used as base and toluene as solvent, the catalyst system exhibited high efficiency for the coupling reaction of the activated aryl halides. When NaH was used as base and o-xylene as solvent, unactivated aryl halides can be used as substrates.
- Zhang, Yi,Ni, Gang,Li, Chengjun,Xu, Sheng,Zhang, Zhaoguo,Xie, Xiaomin
-
p. 4927 - 4932
(2015/06/23)
-
- Discovery of benzylisothioureas as potent divalent metal transporter 1 (DMT1) inhibitors
-
Inhibition of intestinal brush border DMT1 offers a novel therapeutic approach to the prevention and treatment of disorders of iron overload. Several series of diaryl and tricyclic benzylisothiourea compounds as novel and potent DMT1 inhibitors were discovered from the original hit compound 1. These compounds demonstrated in vitro potency against DMT1, desirable cell permeability properties and a dose-dependent inhibition of iron uptake in an acute rat model of iron hyperabsorption. Tricyclic compounds increased the in vitro potency by up to 16-fold versus the original hit. Diaryl compounds 6b and 14a demonstrated significant iron absorption inhibition in vivo with both 25 and 50 mg/kg doses. The diaryl and tricyclic compounds described in this report represent promising structural templates for further optimization.
- Zhang, Zaihui,Kodumuru, Vishnumurthy,Sviridov, Serguei,Liu, Shifeng,Chafeev, Mikhail,Chowdhury, Sultan,Chakka, Nagasree,Sun, Jianyu,Gauthier, Simon J.,Mattice, Maryanne,Ratkay, Laszlo G.,Kwan, Rainbow,Thompson, Jay,Cutts, Alison Brownlie,Fu, Jianmin,Kamboj, Rajender,Goldberg, Y. Paul,Cadieux, Jay A.
-
scheme or table
p. 5108 - 5113
(2012/08/28)
-
- PROCESS FOR THE CATALYTIC SYNTHESIS OF DIARYL ETHERS
-
Described is a process for preparing diaryl ethers of the formula (I) [in-line-formulae]Ar—O—Ar′??(I)[/in-line-formulae]In which Ar is an aryl or substituted aryl group and Ar′ is an aryl, substituted aryl, heteroaryl or substituted heteroaryl group,by reacting an aryl of formula (II) or a aryloxy salt of formula (III) [in-line-formulae]Ar—OH ??(II)[/in-line-formulae] [in-line-formulae]Ar—OR ??(III)[/in-line-formulae]In which Ar has the same meaning as in formula (I) and R is an alkali metal,with an aryl or heteroaryl bromide of formula (IV) [in-line-formulae]Ar′—Br ??(IV)[/in-line-formulae]In which Ar′ has the same meaning as in formula (I),characterized in that the reaction is carried out in the presence of a copper(I)salt and a 1-substituted imidazole as catalyst system.
- -
-
Page/Page column 3; 5
(2009/06/27)
-
- Homocoupling of arylboronic acids catalyzed by 1,10-phenanthroline-ligated copper complexes in air
-
The efficient homocoupling of arylboronic acids was achieved by using the catalytic combination of inexpensive copper salts and 1,10-phenanthroline as aligand. The homocoupling reaction proceeds at ambient temperature in air without any additives such as base or oxidant. This method tolerates various substituents on the arylboronic acids such as halogens, carbonyls, and a nitro group. As a result, 25 symmetrical biaryls were obtained from readily available arylboronic acids in 19-92% isolated yields. A binuclear (μ- hydroxido)copper complex is assumed as the catalytically active species, which undergoes efficient transmetalation with arylboronic acids to produce dinuclear arylcopper complexes. The binuclear structure is assumed to be essential for the bimetallic reductive elimination of biaryls as well as the oxidative restoration of the catalyst. Wiley-VCH Verlag GmbH & Co, KGaA.
- Kirai, Naohiro,Yamamoto, Yoshihiko
-
experimental part
p. 1864 - 1867
(2009/08/17)
-
- Tris-(2-aminoethyl) amine as a novel and efficient tripod ligand for a copper(I)-catalyzed C-O coupling reaction
-
We have introduced a novel, efficient, commercially available and economically attractive N-donor tripod ligand, tris-(2-aminoethyl)amine for copper-catalyzed Ullmann diaryl ether synthesis. This catalyst system is highly active for both aryl iodides and aryl bromides. Variously substituted diaryl ethers have been synthesized in good to excellent yields.
- Jogdand, Nivrutti R.,Shingate, Bapurao B.,Shingare, Murlidhar S.
-
experimental part
p. 4019 - 4021
(2009/11/30)
-
- Bio-inspired copper catalysts for the formation of diaryl ethers
-
Aryl bromides and phenols are coupled efficiently to the corresponding diaryl ethers in the presence of a practical Cu(I)/1-butylimidazole catalyst system. The convenient protocol is applied successfully to the synthesis of 16 different diaryl ethers in high yield and selectivity.
- Schareina, Thomas,Zapf, Alexander,Cotté, Alain,Müller, Nikolaus,Beller, Matthias
-
p. 1851 - 1855
(2008/09/18)
-
- Copper-catalyzed Ullmann coupling under ligand- and additive- free conditions. Part 1: O-Arylation of phenols with aryl halides
-
O-Arylation of a wide variety of substituted phenols and aliphatic alcohols with aryl halides catalyzed by copper iodide under mild ligand and additive free conditions (nBu4NBr, DMF, K3PO4, reflux, 22 h) is accomplished in good to excellent product yields (up to 95%).
- Chang, Joyce Wei Wei,Chee, Sheena,Mak, Shiya,Buranaprasertsuk, Pongchart,Chavasiri, Warinthorn,Chan, Philip Wai Hong
-
p. 2018 - 2022
(2008/09/19)
-
- Synthesis of diaryl ethers through the copper-catalyzed arylation of phenols with aryl iodides using KF/Al2O3
-
An efficient synthesis of diaryl ethers by the copper-catalyzed arylation of phenols with a variety of aryl iodide susing KF/Al2O3 as a suitable base and CuI and 1,3 diphenyl-1,3 propandione as the catalyst is described. Copyright Taylor & Francis Group, LLC.
- Hosseinzadeh, Rahman,Tajbakhsh, Mahmood,Mohadjerani, Maryam,Rezaei, Parizad,Alikarami, Mohammad
-
p. 3023 - 3031
(2008/12/23)
-
- Method of forming a carbon-carbon or carbon-heteroatom linkage
-
The invention relates to a method of creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound. More specifically, the invention relates to the creation of a carbon-nitrogen linkage involving the arylation of nitrogenous organic derivatives. The inventive method consists in creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound providing a carbon atom or a heteroatom (HE) capable of being substituted for the leaving group, thereby creating a C—C or C-HE linkage. The invention is characterised in that the reaction is carried out in the presence of an effective quantity of a catalyst based on copper and at least one ligand comprising at least one imine function and at least one additional nitrogen atom as chelating atoms
- -
-
Page/Page column 37-38
(2010/02/14)
-
- BISPHOSPHINE, PROCESS FOR PRODUCING THE SAME, AND USE THEREOF
-
Bisphosphines represented by the general formula (I) wherein Ar1 and Ar2 each represents an arylene group which may be substituted; R1 and R2 each represents an alkyl group which may be substituted, or an aryl group which may be substituted, or R1 and R2 may combinedly form a ring together with the phosphorus atom bonded thereto; R3 and R4 each represents hydrogen atom or an alkyl group; and the carbon atoms each having R3 and R4 are bonded in positions ortho to the oxygen atom bonded to Ar1 and Ar2: process for production thereof; Group VIII metal complexes comprising said bisphosphines; and process for producing aldehydes, which comprises, on hydroformylation of ethylenically unsaturated compounds with carbon monoxide and hydrogen, using said Group VIII metal complexes.The hydroformylation of ethylenically unsaturated compounds according to the present invention can produce n-aldehydes at higher reaction rate and industrially more advantageously than with catalysts comprising conventional phosphines, while suppressing side reactions such as hydrogenation and isomerization.
- -
-
-
- A general and mild Ullmann-type synthesis of diaryl ethers
-
(Equation presented) An efficient method for the synthesis of diaryl ethers under particularly mild conditions is described. Inexpensive ligands were found to greatly accelerate the Ullmann-type coupling of aryl bromides or iodides with phenols. A series of diaryl ethers were obtained with excellent yields in acetonitrile in the presence of Cs2CO3 and catalytic copper(I) oxide. The reaction tolerates substrates with unfavorable substitution patterns, such as sterically hindered coupling partners or electron-rich aryl halides.
- Cristau, Henri-Jean,Cellier, Pascal P.,Hamada, Samy,Spindler, Jean-Francis,Taillefer, Marc
-
p. 913 - 916
(2007/10/03)
-
- Synthesis of symmetrical diaryl ethers from arylboronic acids mediated by copper(II) acetate
-
Copper promoted generation of phenols in situ through arylation of water and their subsequent arylation with arylboronic acids affords a wide range of symmetrical diaryl ethers in good to high yield. The reaction is rapid, mild, convenient and tolerant of a wide range of functionalities on the arylboronic acid.
- Sagar,Tale,Adude
-
p. 7061 - 7063
(2007/10/03)
-
- Process for arylating or vinylating or alkynating a nucleophilic compound
-
The present invention concerns a process for arylating or vinylating or alkynating a nucleophilic compound. More particularly, the invention concerns arylating nitrogen-containing organic derivatives. The arylating or vinylating or alkynating process of the invention consists of reacting a nucleophilic compound with a compound carrying a leaving group and is characterized in that the reaction is carried out in the presence of an effective quantity of a catalyst based on a metallic element M selected from groups (VIII), (Ib) and (IIb) of the periodic table and at least one ligand comprising at least one imine function and at least one supplemental nitrogen atom as the chelating atoms.
- -
-
-
- Synthesis of diaryl ethers using an easy-to-prepare, air-stable, soluble copper(I) catalyst
-
We have found that bromo(triphenylphosphine)copper(I), an air-stable and soluble copper(I) complex, can be used as a catalyst in the synthesis of diaryl ethers. Using this catalyst, we have synthesized diaryl ethers from electron-rich aryl bromides and electron-rich phenols in the presence of cesium carbonate, in 17-24 h, in NMP. We also found that electron-deficient aryl bromides couple with phenols in the presence of cesium carbonate, in 6 h in NMP at 70°C, without the catalyst.
- Gujadhur,Venkataraman
-
p. 2865 - 2879
(2007/10/03)
-
- Formation of aryl-nitrogen, aryl-oxygen, and aryl-carbon bonds using well-defined copper(I)-based catalysts
-
(Matrix Presented) We report mild synthetic protocols for the formation of aryl-carbon, aryl-nitrogen, and aryl-oxygen bonds based on soluble, well-defined copper(I) catalysts. These protocols do not require the use of palladium and/or expensive ligands.
- Gujadhur, Rattan K.,Bates, Craig G.,Venkataraman
-
p. 4315 - 4317
(2007/10/03)
-
- Catalytic alternative of the Ullman reaction
-
Symmetrical functionalized biaryls and biheterocycles could be obtained in good yield via homocoupling of aryl halides by using Pd(OAc)2 as catalyst with base and isopropanol. This alternative of the Ullmann reaction has proved to be compatible with sensitive functional groups.
- Hassan, Jwanro,Penalva, Vincent,Lavenot, Laurence,Gozzi, Christel,Lemaire, Marc
-
p. 13793 - 13804
(2007/10/03)
-
- Phosphazene P4-But base for the Ullmann biaryl ether synthesis
-
In the presence of phosphazene P4-But base and CuBr, aryl halides couple with phenols to give biaryl ethers at ca. 100 °C.
- Palomo, Claudio,Oiarbide, Mikel,Lopez, Rosa,Gomez-Bengoa, Enrique
-
p. 2091 - 2092
(2007/10/03)
-
- Process for epoxidation of olefinically-unsaturated compounds
-
The invention provides a process for epoxidizing an olefinic double bond in an olefinically-unsaturated compound by contact of a liquid phase mixture containing the olefinically-unsaturated compound, an aldehyde having at least two carbon atoms and a suitable solvent with molecular oxygen in the presence of a catalyst which is soluble in the reaction mixture and which comprises a praseodymium compound. The process has particularly advantageous application to oxidation of aldrin to dieldrin.
- -
-
-
- DEBROMINATION OF PHENACYL AND BENZYLIC BROMIDES WITH TERTIARY STIBINE AND THE MECHANISTIC CONSIDERATION
-
Tributylstibine is an efficient reagent for debromination of phenacyl and arylmethyl bromides.The mechanistic difference between stibine and phosphine is discussed briefly.
- Akiba, Kin-ya,Shimizu, Akiyoshi,Ohnari, Hideyuki,Ohkata, Katsuo
-
p. 3211 - 3214
(2007/10/02)
-
- Neutral Ionophores with Selectivity for Na+
-
New non-macrocyclic, electrically neutral ionophores 5 - 9 are described.In membranes they induce selectivities of Na+ over K+ by a factor of up to 20.
- Voegtle, Fritz,Kleiner, Thomas,Leppkes, Reinhard,Laeubli, Markus Werner,Ammann, Daniel,Simon, Wilhelm
-
p. 2028 - 2034
(2007/10/02)
-
