- Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction
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A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl-S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl-Ni-SR and aryl-Ni-OAr species to furnish aryl exchanged compounds.
- Isshiki, Ryota,Kurosawa, Miki B.,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 10333 - 10340
(2021/07/21)
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- Mechanochemical Solvent-Free Catalytic C?H Methylation
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The mechanochemical, solvent-free, highly regioselective, rhodium-catalyzed C?H methylation of (hetero)arenes is reported. The reaction shows excellent functional-group compatibility and is demonstrated to work for the late-stage C?H methylation of biologically active compounds. The method requires no external heating and benefits from considerably shorter reaction times than previous solution-based C?H methylation protocols. Additionally, the mechanochemical approach is shown to enable the efficient synthesis of organometallic complexes that are difficult to generate conventionally.
- Ni, Shengjun,Hribersek, Matic,Baddigam, Swarna K.,Ingner, Fredric J. L.,Orthaber, Andreas,Gates, Paul J.,Pilarski, Lukasz T.
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supporting information
p. 6660 - 6666
(2020/12/18)
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- Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
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Paragraph 0134-0138; 0140
(2021/05/29)
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- Benzylic C?H Functionalisation by [Et3SiH+KOtBu] leads to Radical Rearrangements in o-tolyl Aryl Ethers, Amines and Sulfides
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Reaction of Et3SiH+KOtBu with diaryl ethers, sulfides and amines that feature an ortho alkyl group leads to rearrangement products. The rearrangements arise from formation of benzyl radicals, likely formed through hydrogen atom abstraction by triethylsilyl radicals. The rearrangements involve cyclisation of the benzyl radical onto the partner arene, which, from computation, is the rate determining step. In the case of diaryl ethers, Truce-Smiles rearrangements arise from radical cyclisations to form 5-membered rings, but for diarylamines, cyclisations to form dihydroacridines are observed. (Figure presented.).
- Arokianathar, Jude N.,Kolodziejczak, Krystian,Bugden, Frances E.,Clark, Kenneth F.,Tuttle, Tell,Murphy, John A.
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supporting information
p. 2260 - 2267
(2020/05/06)
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- A directing group-assisted ruthenium-catalyzed approach to access: Meta -nitrated phenols
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meta-Selective C-H nitration of phenol derivatives was developed using a Ru-catalyzed σ-activation strategy. Cu(NO3)2·3H2O was employed as the nitrating source, whereas Ru3(CO)12 was found to be the most suitable metal catalyst for the protocol. Mechanistic studies suggested involvement of an ortho-CAr-H metal intermediate, which promoted meta-electrophilic aromatic substitution and silver-assisted free-radical pathway.
- Sasmal, Sheuli,Sinha, Soumya Kumar,Lahiri, Goutam Kumar,Maiti, Debabrata
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supporting information
p. 7100 - 7103
(2020/07/14)
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- N - And O -arylation of pyridin-2-ones with diaryliodonium salts: Base-dependent orthogonal selectivity under metal-free conditions
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Metal-free N- and O-arylation reactions of pyridin-2-ones as ambident nucleophiles have been achieved with diaryliodonium salts on the basis of base-dependent chemoselectivity. In the presence of N,N-diethylaniline in fluorobenzene, pyridin-2-ones were very selectively converted to N-arylated products in high yields. On the other hand, the O-arylation reactions smoothly proceeded with the use of quinoline in chlorobenzene, leading to high yields and selectivities. In these methods, a variety of pyridin-2-ones in addition to pyridin-4-one and a set of diaryliodonium salts were accepted as suitable reaction partners.
- Abe, Yusuke,Hanazawa, Natsumi,Katagiri, Kotone,Kuriyama, Masami,Ono, Shimpei,Onomura, Osamu,Yamamoto, Kosuke
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p. 8295 - 8300
(2020/09/09)
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- Identification of an Oxalamide Ligand for Copper-Catalyzed C?O Couplings from a Pharmaceutical Compound Library
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A typical pharmaceutical compound library is stocked with molecular diversity and could provide a platform for the discovery of new ligand structures. Herein, we describe the use of this approach in combination with high throughput screening to identify N,N’-bis(thiophene-2-ylmethyl)oxalamide as a ligand that is generally effective for copper-catalyzed C?O cross-couplings to prepare both biarylethers as well as phenols under mild conditions.
- Chan, Vincent S.,Krabbe, Scott W.,Li, Changfeng,Sun, Lijie,Liu, Yue,Nett, Alex J.
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- Transition-Metal-Catalyzed Transformation of Sulfonates via S-O Bond Cleavage: Synthesis of Alkyl Aryl Ether and Diaryl Ether
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The catalytic conversion of sulfonates, a versatile class of pharmaceutical intermediates, is usually based on C-O bond cleavage. In this paper, however, we discover a rare transformation of sulfonates via S-O bond cleavage catalyzed by transition metal, through which alkyl sulfonates could undergo an intramolecular desulfitative C-O coupling to form aryl alkyl ethers in the presence of a nickel catalyst. Meanwhile, aryl sulfonates perform similarly to give diaryl ethers catalyzed by a palladium complex. This transformation could tolerate a wide range of functionalities. Controlled experiments reveal that the 2-pyridyl group is necessary to promote the reaction as designed. Crossover experiments proved that this transformation might proceed partly in an intermolecular pathway.
- Chen, Xuemeng,Xiao, Xue,Sun, Haotian,Li, Yue,Cao, Haolin,Zhang, Xuemei,Yang, Shengyong,Lian, Zhong
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supporting information
p. 8879 - 8883
(2019/11/14)
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- Substituent Effects of 2-Pyridones on Selective O-Arylation with Diaryliodonium Salts: Synthesis of 2-Aryloxypyridines under Transition-Metal-Free Conditions
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An efficient transition-metal-free strategy to synthesize 2-aryloxypyridine derivatives has been developed by a selective O-arylation of 2-pyridones with diaryliodonium salts. The reaction was compatible with a series of functional groups for 2-pyridones and diaryliodonium salts such as halides, nitro, cyano, and ester groups. The substituents at the C6-position of 2-pyridones favored O-arylation products because of steric hindrance. The reaction was easily performed on a gram-scale and 6-chloro-2-pyridone was a good precursor to access various unsubstituted 2-aryloxypyridines by dehalogenation. A P2Y 1 lead compound analogue could be prepared in good yield over two steps.
- Li, Xiao-Hua,Ye, Ai-Hui,Liang, Cui,Mo, Dong-Liang
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p. 1699 - 1710
(2018/02/06)
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- A ortho-nitro phenol and its derivative synthesis method (by machine translation)
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The invention relates to a method for the synthesis of organic compounds, in the existing technology of O-nitrophenol strong acid used in the synthesis process of the serious problem of environmental pollution and the synthesis step longer more complicated problem, the invention provides a ortho-nitro phenol and synthetic method of derivative thereof, proceeding by the phenol compound, synthesis of 2 - (phenoxy) pyridine, the obtained product, catalyst, tert-butyl nitrite, organic solvent and adding sealing in the pressure containers, in oil bath heating 50 - 100 °C, reaction 10 - 30 hours, to obtain 2 - (2 - nitrobenzene) ethoxy pyridine; re-processing by the ortho-nitro phenol and its derivatives; the method is simple, high-efficiency. (by machine translation)
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Paragraph 0092
(2017/08/23)
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- Synthesis of m-Alkylphenols via a Ruthenium-Catalyzed C-H Bond Functionalization of Phenol Derivatives
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The first example of the synthesis of m-alkylphenols via a ruthenium-catalyzed CAr-H bond functionalization of phenol derivatives with sec/tert-alkyl bromides is reported. Mechanistic studies indicated that the m-CAr-H bond alkylation may involve a radical process and that a six-membered ruthenacycle complex was the active catalyst. Moreover, this approach can provide an expedited strategy for the atom-/step-economical synthesis of many noteworthy pharmaceuticals and other functional molecules.
- Li, Gang,Gao, Panpan,Lv, Xulu,Qu, Chen,Yan, Qingkai,Wang, Ya,Yang, Suling,Wang, Junjie
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supporting information
p. 2682 - 2685
(2017/05/24)
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- An ortho-nitro phenol synthetic method of compound
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The invention relates to a synthesis method of o-nitrophenol compounds, solving the problems that production hazards are easily caused due to the release of a large deal of heat during the synthesis of o-nitrophenol and the severe environment pollution caused due to the generation of a large deal of waste gas and acid in the process in the prior art. The invention provides the synthesis method of the o-nitrophenol compounds, which comprises the steps: synthesizing 2-(phenoxy)pyridine from phenol compounds; and then sequentially adding 2-(phenoxy)pyridine and a catalyst, a nitrating reagent, an oxidant and an organic solvent into a sealed pressure container, heating and reacting for 10-50 hours in an oil bath of which the temperature is 80 DEG C-130 DEG C to obtain 2-(2-nitrophenyl)oxy pyridine; and finally treating to obtain o-nitrophenol. The synthesis method is simple, convenient and efficient.
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Paragraph 0092
(2016/10/10)
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- Rhodium-catalyzed borylation of aryl 2-pyridyl ethers through cleavage of the carbon-oxygen bond: Borylative removal of the directing group
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The rhodium-catalyzed reaction of aryl 2-pyridyl ethers with a diboron reagent results in the formation of arylboronic acid derivatives via activation of the C(aryl)-O bonds. The straightforward synthesis of 1,2-disubstituted arenes was enabled through catalytic ortho C-H bond functionalization directed by the 2-pyridyloxy group followed by substitution of this group with a boryl group. Several control experiments revealed that the presence of a sp2 nitrogen atom at the 2-position of the substrate and the use of a boron-based reagent were crucial for the activation of the relatively inert C(aryl)-O bond of aryl 2-pyridyl ethers.
- Kinuta, Hirotaka,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 1593 - 1600
(2015/03/05)
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- C-H functionalization of phenols using combined ruthenium and photoredox catalysis: In situ generation of the oxidant
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A combination of ruthenium and photoredox catalysis allowed the ortho olefination of phenols. Using visible light, the direct C-H functionalization of o-(2-pyridyl) phenols occurred, and diverse phenol ethers were obtained in good yields. The regeneration of the ruthenium catalyst was accomplished by a photoredox-catalyzed oxidative process.
- Fabry, David C.,Ronge, Meria A.,Zoller, Jochen,Rueping, Magnus
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supporting information
p. 2801 - 2805
(2015/03/04)
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- Chemoselective and ligand-free synthesis of diaryl ethers in aqueous medium using recyclable alumina-supported nickel nanoparticles
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An economical and eco-compatible ligand-free protocol for the synthesis of diaryl ethers has been developed using easily accessible alumina-supported nickel nanoparticles as a stable recyclable heterogeneous catalyst in aqueous medium along with a surfactant (SDS) and a mild base (K2CO3). Various sensitive functional groups like allyl, alkoxycarbonyl, formyl, oxo, chloro, bromo, amine and nitro were tolerated in the aforesaid method. Excellent chemoselectivity was demonstrated through competition experiments.
- Ghatak, Avishek,Khan, Sagar,Roy, Rimi,Bhar, Sanjay
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supporting information
p. 7082 - 7088
(2015/02/02)
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- Palladium-catalyzed oxidative olefination of phenols bearing removable directing groups under molecular oxygen
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An efficient Pd(II)-catalyzed oxidative olefination of phenols bearing removable directing groups with molecular oxygen as the sole oxidant has been developed. This reaction protocol provides an efficient and robust synthetic tool for the synthesis of o-alkenyl phenols under mild conditions.
- Liu, Bin,Jiang, Huai-Zhi,Shi, Bing-Feng
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supporting information
p. 1521 - 1526
(2014/03/21)
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- Pd(ii)-catalyzed oxidative alkoxycarbonylation of 2-phenoxypyridine derivatives with CO and alcohols
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A Pd(ii)-catalyzed oxidative alkoxycarbonylation of phenol derivatives with atmospheric pressure of CO-O2 and alcohols has been achieved. The reaction provides an efficient strategy for the synthesis of carboxylic esters and can be applied to the late-stage modification of complex molecules. This journal is the Partner Organisations 2014.
- Liu, Bin,Jiang, Huai-Zhi,Shi, Bing-Feng
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supporting information
p. 2538 - 2542
(2014/04/17)
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- Palladium-catalyzed decarboxylative coupling of α-oxocarboxylic acids with C(sp2)-H of 2-aryloxypyridines
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An efficient palladium-catalyzed decarboxylative ortho-acylation of 2-aryloxypyridines with α-oxocarboxylic acids is described. In this new transformation, the aromatic C(sp2)-H bond was successfully acylated to give diverse aromatic ketones regioselectively in moderate to good yields. The pyridine group can be removed easily after the acylation to give the corresponding 2-hydroxy aromatic ketones. Copyright
- Yao, Jinzhong,Feng, Ruokun,Wu, Zaihong,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 1517 - 1522
(2013/06/27)
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- PROCESS FOR THE CATALYTIC SYNTHESIS OF DIARYL ETHERS
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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.
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Page/Page column 3; 5
(2009/06/27)
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- (2-Pyridyl)acetone-promoted Cu-catalyzed O-arylation of phenols with aryl iodides, bromides, and chlorides
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(Chemical Equation Presented) Employing (2-pyridyl)acetone as a new supporting ligand, the copper-catalyzed coupling reactions of aryl chlorides, aryl bromides, and aryl iodides with various phenols successfully proceeded in good yields under mild conditions. This reaction displays great functional groups compatibility and excellent reactive selectivity.
- Zhang, Qi,Wang, Deping,Wang, Xianyang,Ding, Ke
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supporting information; experimental part
p. 7187 - 7190
(2009/12/09)
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- Bio-inspired copper catalysts for the formation of diaryl ethers
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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
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p. 1851 - 1855
(2008/09/18)
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- Cu-catalyzed N- and O-arylation of 2-,3-, and 4-hydroxypyridines and hydroxyquinolines
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With use of Cu-based catalysts, 2- and 4-hydroxypyridines were N-arylated in modest to excellent yields. In the case of 2-hydroxypyridine, the use of 4,7-dimethoxy-1,10-phenanthroline, 3, expanded the scope of previous literature reports to include the use of N-containing heteroaryl halides, and 2-substituted aryl halides. In addition, by using a copper catalyst based on 2,2,6,6-tetramethylheptane-3,5-dione, 4, the first N-arylations of 4-hydroxypyridines and O-arylations of 3-hydroxypyridines with aryl bromides and iodides have been accomplished.
- Altman, Ryan A.,Buchwald, Stephen L.
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p. 643 - 646
(2008/02/03)
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