- Ligand- and Counterion-Assisted Phenol O-Arylation with TMP-Iodonium(III) Acetates
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High reactivity of trimethoxyphenyl (TMP)-iodonium(III) acetate for phenol O-arylation was achieved. It was first determined that the TMP ligand and acetate anion cooperatively enhance the electrophilic reactivity toward phenol oxygen atoms. The proposed method provides access to various diaryl ethers in significantly higher yields than the previously reported techniques. Various functional groups, including aliphatic alcohol, boronic ester, and sterically hindered groups, were tolerated during O-arylation, verifying the applicability of this ligand- and counterion-assisted strategy.
- Kikushima, Kotaro,Miyamoto, Naoki,Watanabe, Kazuma,Koseki, Daichi,Kita, Yasuyuki,Dohi, Toshifumi
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supporting information
p. 1924 - 1928
(2022/03/27)
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- Diaryl Ether Formation Merging Photoredox and Nickel Catalysis
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Photoredox and Ni catalysis are combined to produce diaryl ethers under mild conditions. A broad range of aryl halides and phenol derivatives are cross-coupled in the presence of a readily available organic photocatalyst and NiBr2(dtbpy). Symmetrical diaryl ethers have also been directly obtained from aryl bromides in the presence of water. Mechanistic investigations support the involvement of Ni(0) species at the outset of the reaction and a Ni(II)/Ni(III)-photocatalyzed single electron transfer process preceding the productive C(sp2)-OAr reductive elimination.
- Liu, Le,Nevado, Cristina
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supporting information
p. 2188 - 2193
(2021/05/04)
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- The Suzuki-Miyaura Coupling of Nitroarenes
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Synthesis of biaryls via the Suzuki-Miyaura coupling (SMC) reaction using nitroarenes as an electrophilic coupling partners is described. Mechanistic studies have revealed that the catalytic cycle of this reaction is initiated by the cleavage of the aryl-nitro (Ar-NO2) bond by palladium, which represents an unprecedented elemental reaction.
- Yadav, M. Ramu,Nagaoka, Masahiro,Kashihara, Myuto,Zhong, Rong-Lin,Miyazaki, Takanori,Sakaki, Shigeyoshi,Nakao, Yoshiaki
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supporting information
p. 9423 - 9426
(2017/07/24)
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- Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
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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
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p. 13249 - 13258
(2017/09/12)
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- Nickel-Catalyzed Deamidative Step-Down Reduction of Amides to Aromatic Hydrocarbons
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To date, cleavage of the C-N bond in aromatic amides has been achieved in molecules with a distorted constitutional framework around the nitrogen atom. In this report, a nickel-catalyzed reduction of planar amides to the corresponding lower hydrocarbon homologue has been reported. This involves a one-pot reductive cleavage of the C-N bond followed by a tandem C-CO bond break in the presence of a hydride source. Substrate scope circumscribes deamidation examples which proceed via oxidative addition of nickel in the amide bonds of nontwisted amides. Mechanistic studies involving isolation and characterization of involved intermediates via different spectroscopic techniques reveal a deeper introspection into the plausible catalytic cycle for the methodology.
- Dey, Aniruddha,Sasmal, Sheuli,Seth, Kapileswar,Lahiri, Goutam Kumar,Maiti, Debabrata
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p. 433 - 437
(2017/06/05)
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- Visible-light-mediated synthesis of diaryl ethers from arylboronic acids and diaryliodonium salts
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With visible-light irradiation, a simple and metal-free photocatalytic system for the synthesis of diaryl ethers from arylboronic acids and diaryliodonium salts has been developed. The reaction proceeded in high yield for a range of different substrates in the presence of eosin Y under mild reaction conditions.
- Liu, Li,Tang, Jiaqi,Qiang, Jian,Li, Jian,He, Mingyang
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p. 261 - 264
(2016/07/06)
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- Synthesis of benzannulated heterocycles by twofold Suzuki-Miyaura couplings of cyclic diarylborinic acids
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Two-fold Suzuki-Miyaura cross-couplings of cyclic diarylborinic acids are described. This novel annulation method enables the synthesis of benzo-fused heterocycles from dihaloarenes or gem-dibromoolefins.
- Dimitrijevic, Elena,Cusimano, Madeline,Taylor, Mark S.
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supporting information
p. 1391 - 1394
(2014/03/21)
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- Reactions of enantiopure cyclic diols with sulfuryl chloride
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Monocyclic allylic cis-1,2-diols reacted with sulfuryl chloride at 0 °C in a regio- and stereo-selective manner to give 2-chloro-1-sulfochloridates, which were hydrolysed to yield the corresponding trans-1,2-chlorohydrins. At -78 °C, with very slow addition of sulfuryl chloride, cyclic sulfates were formed in good yields, proved to be very reactive with nucleophiles and rapidly decomposed on attempted storage. Reaction of a cyclic sulfate with sodium azide yielded a trans-azidohydrin without evidence of allylic rearrangement occurring. An enantiopure bicyclic cis-1,2-diol reacted with sulfuryl chloride to give, exclusively, a trans-1,2-dichloride enantiomer with retention of configuration at the benzylic centre and inversion at the non-benzylic centre; a mechanism is presented to rationalise the observation.
- Boyd, Derek R.,Sharma, Narain D.,Kaik, Magdalena,McIntyre, Peter B.A.,Malone, John F.,Stevenson, Paul J.
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p. 2128 - 2136
(2014/03/21)
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- General method for functionalized polyaryl synthesis via aryne intermediates
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A method for base-promoted arylation of arenes and heterocycles by aryl halides and aryl triflates is described. Additionally, in situ electrophilic trapping of ArLi intermediates generated in the reaction of benzyne with deprotonated arenes or heterocycles has been developed, providing rapid and easy access to a wide range of highly functionalized polyaryls. Base-promoted arylation methodology complements transition-metal-catalyzed direct arylation and allows access to structures that are not easily accessible via other direct arylation methods. The reactions are highly functional-group tolerant, with alkene, ether, dimethylamino, trifluoromethyl, ester, cyano, halide, hydroxyl, and silyl functionalities compatible with reaction conditions.
- Truong, Thanh,Mesgar, Milad,Le, Ky Khac Anh,Daugulis, Olafs
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supporting information
p. 8568 - 8576
(2014/07/07)
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- Solar energy assisted synthesis of palladium nanoplates and its application in 2-phenoxy-1,1′-biphenyls and N,N-dimethyl-[1,1′-biphenyl] derivatives synthesis
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Present work aims to develop a greener approach for the palladium nanoplates (PdNPs) synthesis and its catalytic applications. The protocol deals with solar energy assisted ionic palladium reduction in the presence of polyvinylpyrrolidone (PVP) and ethylene glycol (EG) with a good shape selectivity. Polyvinylpyrrolidone plays a duel role of capping agent and mild reductant; whereas, ethylene glycol acts as a reductant and solvent. The optimum sunlight concentration is a key factor to the anticipated nanoplate's synthesis. Results show that the most of nanoparticles are hexagonal and triangular nanoplates in the range of 20-50 nm. This is a first report which shows ~70% selectivity to the nanoplates formation using sun light. The study also covers it's catalytic application, wherein; 2-phenoxy-1,1′- biphenyls and N,N-dimethyl-[1,1′-biphenyl] derivatives were synthesized by a simple, ligand free, faster, one pot, ecological and economic protocol in aqueous medium. The catalyst shows better performance than that of conventionally available 10% Pd/C catalyst. The prepared PdNPs showed excellent catalytic performance to the desired products with recyclability.
- Patil, Aniruddha B.,Bhanage, Bhalchandra M.
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- Palladium-catalyzed arylation of simple arenes with iodonium salts
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The development of an arylation protocol for simple arenes with diaryliodonium salts using the Herrmann-Beller palladacycle catalyst is reported. The reaction takes simple aromatic feedstocks and creates valuable biaryls for use in all sectors of the chem
- Storr, Thomas E.,Greaney, Michael F.
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supporting information
p. 1410 - 1413
(2013/05/09)
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- An Ullmann C-O coupling reaction catalyzed by magnetic copper ferrite nanoparticles
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Herein, an efficient method for the Ullmann C-O coupling reaction between various kinds of phenols and aryl halides, including amino, ketone, cyano, methyl, methoxy, fluoro, chloro and bromo derivatives, is described. The catalyst used, copper ferrite (CuFe2O4) nanoparticles, are easily made, air-stable, and of low cost. The catalyst can be recycled easily just by using an external magnet. Even in the presence of sensitive substituents, the reaction proceeds successfully to provide the desired products in high yields without protection of other functional groups. Copyright
- Yang, Shuliang,Wu, Cunqi,Zhou, Hua,Yang, Yanqin,Zhao, Yongxia,Wang, Chenxu,Yang, Wei,Xu, Jingwei
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supporting information
p. 53 - 58
(2013/03/13)
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- Metal-free arylation of oxygen nucleophiles with diaryliodonium salts
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Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho- and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy. Copyright
- Jalalian, Nazli,Petersen, Tue B.,Olofsson, Berit
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p. 14140 - 14149,10
(2012/12/12)
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- Metal- and ligand-free Ullmann-type C-O and C-N coupling reactions promoted by potassium tert-butoxide
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A simple, metal- and ligand-free procedure for the Ullmann-type C-O coupling reactions has been achieved by allowing aryl bromides to react with a variety of phenols in the presence of t-BuOK. Moderate to excellent yields of O-arylation products are obtained under mild conditions in a short time. In addition, two examples of C-N coupling reactions are also reported. A benzyne mechanism is proposed according to the experiment data.
- Yang, Shuliang,Wu, Cunqi,Ruan, Mingbo,Yang, Yanqin,Zhao, Yongxia,Niu, Jiajia,Yang, Wei,Xu, Jingwei
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supporting information; experimental part
p. 4288 - 4292
(2012/09/22)
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- Well-defined air-stable palladium HASPO complexes for efficient Kumada-Corriu cross-couplings of (Hetero)aryl or alkenyl tosylates
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Palladium complexes of representative heteroatom-substituted secondary phosphine oxide (HASPO) preligands were synthesized and fully characterized, including X-ray crystal structure analysis. Importantly, these well-defined complexes served as highly efficient catalysts for Kumada-Corriu cross-coupling reactions of aryl, alkenyl, and even heteroaryl tosylates. Particularly, an air-stable catalyst derived from inexpensive PinP(O)H displayed a remarkably high catalytic efficacy, which resulted in cross-couplings at low catalyst loadings under exceedingly mild reaction conditions with ample scope.
- Ackermann, Lutz,Kapdi, Anant R.,Fenner, Sabine,Kornhaab, Christoph,Schulzke, Carola
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supporting information; experimental part
p. 2965 - 2971
(2011/05/05)
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- Synthesis of diaryl ethers through the copper-catalyzed arylation of phenols with aryl iodides using KF/Al2O3
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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
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p. 3023 - 3031
(2008/12/23)
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- An efficient Ullmann-type C-O bond formation catalyzed by an air-stable copper(I)-bipyridyl complex
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(Chemical Equation Presented) An efficient O-arylation of phenols and aliphatic alcohols with aryl halides was developed that uses an air-stable copper(I) complex as the catalyst. This arylation reaction can be performed in good yield in the absence of Cs2CO3. A variety of functional groups are compatible with these reaction conditions with low catalyst loading levels.
- Niu, Jiajia,Zhou, Hua,Li, Zhigang,Xu, Jingwei,Hu, Shaojing
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p. 7814 - 7817
(2008/12/22)
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- Reactions of Selenurane with Alcohols, Thiols and Selenol. A Quest for Formation of a New ?-Selenurane , or
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Bis(2,2'-biphenylylene)selenurane readily reacts with various alcohols, phenols, thiols and selenol to give ligand coupling or ipso-substitution products under mild conditions via a two-step mechanism involving a ?-selenurane , and or corresponding selenonium salts as intermediates.
- Sato, Soichi,Furukawa, Naomichi
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p. 889 - 892
(2007/10/02)
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- REACTIONS AND MECHANISM OF BIS(2,2'-BIPHENYLYLENE)-SULFURANE WITH THE REAGENTS HAVING HYDROXYL GROUP.
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Bis(2,2'-biphenylylene)sulfurane reacts readily with various alcohols, phenols, and thiols to give ligand coupling or ipso-substitution products under mild cocnditions via a two-step mechanism involving a ?-sulfuranes or corresponding sulfonium salts as intermediates.
- Sato, Soichi,Matsunaga, Yoshi,Kitagawa, Makiko,Furukawa, Naomichi
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p. 447 - 448
(2007/10/02)
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- COPPER CATALYSED O-PHENYLATION OF PHENOLS AND ENOLS BY PENTAVALENT ORGANOBISMUTH COMPOUNDS
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The O-phenylation of phenols under neutral conditions by Bi(V) reagents is strongly catalysed by copper salts and by copper powder, even at room temperature.Enolic systems are also subject to copper powder catalysis and give exclusively O-phenylation.
- Barton, Derek H. R.,Finet, Jean-Pierre,Khamsi, Jamal,Pichon, Clotilde
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p. 3619 - 3622
(2007/10/02)
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- Metalloporphyrin-Catalyzed Decomposition of Cyclic Diperoxides (1,2,4,5-Tetraoxanes)
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Cyclic diperoxides of type 1 (a, R=H; b, R=Ph; c, R=n-Bu; d, R=Me) were found to be very stable (Ea = 42-48 kcal/mol, log A = 17-19).Decomposition of 1 was greatly promoted by addition of ZnTPP or CoTPP, leading to formation of ketone PhCOR and ester (or acid) PhCO2R as the major products.In the presence of PH2S or Ph2SO as oxygen acceptor, the oxygen transfer reaction occurred and the production of PhCO2R (=PhCO2Bu) was completely suppressed in the case of 1c, while it (the production of PhCO2H) was not measurably suppressed in the case of 1a.Chemiluminescence (CL) that is due to singlet ZnTPP formation was detected from the reaction of ZnTPP with 1a but not with 1c.The observed first-order decay rate of CL for the reaction of 1a with ZnTPP and its para-substituted derivatives Zn(p-X)TPP increased with the increase in electron-donating nature of the substituents (CN Cl H CH3 OCH3).A tentative mechanism for this ZnTPP-catalyzed decomposition reaction, which takes the different behaviors of 1a and 1c into account, is proposed.
- Ito, Yoshikatsu,Tone, Mutsuo,Yokoya, Hiroaki,Matsuura, Teruo,Schuster, Gary B.
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p. 2240 - 2245
(2007/10/02)
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