- Recyclable solid ruthenium catalysts for the direct arylation of aromatic C-H bonds
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(Figure Presented) Environmentally benign catalyst: A PPh3-modified Ru/CeO2 catalyst showed excellent catalytic activity toward direct C-H arylation by using various aryl chlorides in the reaction (see scheme). The catalyst was found to act heterogeneously and could be recycled without significant loss of activity.
- Miura, Hiroki,Wada, Kenji,Hosokawa, Saburo,Inoue, Masashi
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- Rhodium/N-heterocyclic carbene catalyzed direct intermolecular arylation of sp2 and sp3 C-H bonds with chelation assistance
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Rh-oadies join in: A new rhodium catalyst was developed for the chelation-assisted direct intermolecular arylation using an N-heterocyclic carbene and phosphine ligands (see scheme; IMes=1,3bis(2,4,6-trimethylphenyl) imidazol-2-ylidene). The reaction is o
- Kim, Min,Kwak, Jaesung,Chang, Sukbok
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- Arene Ruthenium Catalyst MCAT-53 for the Synthesis of Heterobiaryl Compounds in Water through Aromatic C-H Bond Activation
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A new water friendly MCAT-53 [Ru2Cl2 (HCOO)3(p-cymene)] Na (sodium η-6-p-cymene dichloro diruthenium triformato complex) has been developed as a catalyst to effect aromatic C-H bond activation and C-C coupling reactions in
- Mehta, Anita,Saha, Biswajit,Koohang, Ali Aiden,Chorghade, Mukund S.
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- Merging two functions in a single Rh catalyst system: Bimodular conjugate for light-induced oxidative coupling
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A single molecular rhodium catalyst system (PC2-Cp#RhIII) bearing two functional domains for both photosensitization and C-H carbometalation was designed to enable an intramolecular redox process. The hypothesized charge-transfer species (PC2·-Cp#RhIV) was characterized by spectroscopic and electrochemical analyses. This photoinduced internal oxidation allows a facile access to the triplet state of the key post-transmetalation intermediate that readily undergoes C-C bond-forming reductive elimination with a lower activation barrier than in its singlet state, thus enabling catalytic C-H arylation and methylation processes.
- Kim, Jinwoo,Kim, Dongwook,Chang, Sukbok
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Read Online
- Oxidatively Induced Reductive Elimination: Exploring the Scope and Catalyst Systems with Ir, Rh, and Ru Complexes
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Direct conversion of C-H bonds into C-C bonds is a promising alternative to the conventional cross-coupling reactions, thus giving rise to a wide range of efficient catalytic C-H functionalization reactions. Among the elementary stages in the catalytic C-
- Kim, Jinwoo,Shin, Kwangmin,Jin, Seongho,Kim, Dongwook,Chang, Sukbok
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supporting information
p. 4137 - 4146
(2019/03/07)
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- Selective C?N Bond Cleavage of N-Acylisatins: Towards High Performance Acylation/Arylation/Transamination Reagents
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New multipurpose arylation/acylation/transamination reagents, N-acylisatins, have been developed by selective ‘inside-outside’ C?N bond cleavage under different catalytic conditions. As activated amides, N-acylisatins undergo Rh-catalyzed C?H arylation and Pd-catalyzed acylation by cleavage outside the C?N bond, and the desired biaryls and diaryl ketones were obtained in good to excellent yields. Generally, the combination of N-acylisatins with amines leads to a ring-opening reaction and formation of transamination products in a predictable manner through inside C?N bond cleavage. Interestingly, treatment of N-acylisatins with amines lead to unexpected outer-ring transamination products when CsF is added, which shows that CsF can favor the outside C?N bond cleavage path. Notably, this work presents a new strategy for multiple chemical transformations of a single amide to achieve various products by selective C?N bond cleavage. (Figure presented.).
- Xiong, Li,Deng, Rong,Liu, Tingting,Luo, Zhongfeng,Wang, Zijia,Zhu, Xiao-Feng,Wang, Hui,Zeng, Zhuo
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p. 5383 - 5391
(2019/11/03)
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- Expeditious and Solvent-Free Nickel-Catalyzed C?H Arylation of Arenes and Indoles
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An efficient solvent-free nickel-catalyzed method for C?H bond arylation of arenes and indoles has been developed, which proceeds expeditiously through chelation assistance. The reaction is highly selective for mono-arylation and tolerates sensitive and structurally diverse functionalities, such as halides, ethers, amines, indole, pyrrole and carbazole. This reaction represents the first example of a nickel-catalyzed C?H arylation by monochelate assistance and symbolizes a rare precedent in solvent-free C?H arylation. Mechanistic investigations by various controlled reactions, kinetic studies, and deuterium labeling experiments suggest that the arylation follows a single electron transfer (SET) pathway involving the turnover-limiting C?H nickelation process.
- Jagtap, Rahul A.,Soni, Vineeta,Punji, Benudhar
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p. 2242 - 2248
(2017/05/29)
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- Site-selective C-H/C-N activation by cooperative catalysis: Primary amides as arylating reagents in directed C-H arylation
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Direct C-H arylation of nonacidic C(sp)-H bonds with primary amides as arylating reagents via highly chemoselective C-H/C-N/C-C cleavages has been accomplished for the first time. The key to the success is the cooperative combination of rhodium(I) catalys
- Meng, Guangrong,Szostak, Michal
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p. 7251 - 7256
(2017/11/09)
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- Chelation-directed C-H activation/C-C bond forming reactions catalyzed by Pd(II) nanoparticles supported on multiwalled carbon nanotubes
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Chelation-directed C-H activation/C-C bond forming reactions utilizing homogeneous palladium(II) and the Pd(II)/Pd(iv) catalytic cycle have been previously reported. Here we report the first use of a solid-supported Pd(II) catalyst [Pd(II) nanoparticles on multiwalled carbon nanotubes, Pd(II)/MWCNT] to carry out C-H activation/C-C bond forming reactions. The results presented demonstrate that the solid-supported Pd(II)/MWCNT catalyst can effectively catalyze these arylation reactions using the Pd(II)/Pd(iv) catalytic cycle. We also show that the solid-supported catalyst is recyclable, has turnover frequencies up to 2.9-fold higher than the homogeneous catalyst, and results in low levels of residual palladium contamination in the products.
- Korwar, Sudha,Burkholder, Michael,Gilliland, Stanley E.,Brinkley, Kendra,Gupton, B. Frank,Ellis, Keith C.
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p. 7022 - 7025
(2017/07/10)
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- Rhodium-catalyzed C-H functionalization with N-acylsaccharins
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A rhodium-catalyzed C-H functionalization with activated amides by decarbonylation has been developed. Notably, this is the first C-H arylation employing N-acylsaccharins as coupling partners to give biaryls in good to excellent yields. The highlight of the work is the high tolerance of functional groups such as formyl, ester, and vinyl and the use of a removable directing group.
- Wu, Hongxiang,Liu, Tingting,Cui, Ming,Li, Yue,Jian, Junsheng,Wang, Hui,Zeng, Zhuo
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supporting information
p. 536 - 540
(2017/01/25)
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- Efficient Approach to Construct Unsymmetrical Biaryls through Oxidative Coupling Reactions of Aromatic Primary Alcohols and Arylboronic Acids with a Rhodium Catalyst
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Unsymmetrical biaryls were synthesized by oxidative coupling reactions between aromatic primary alcohols and arylboronic acids through the C-C bond cleavage of the primary alcohols chelated with a rhodium catalyst. The desired unsymmetrical biaryl products were obtained in good to excellent yields under the optimized reaction conditions. A wide variety of functionalities are compatible with the reaction under the optimized conditions. This new coupling strategy provides a favorable method to construct valuable biaryl compounds from aromatic primary alcohols which are cheap, environmentally friendly, and easily accessible substrates.
- Yu, Xiaobo,Wang, Jingjing,Guo, Weijie,Tian, Yun,Wang, Jianhui
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supporting information
p. 1876 - 1884
(2016/07/06)
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- Rhodium-Catalyzed C-H Bond Functionalization with Amides by Double C-H/C-N Bond Activation
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The first C-H bond functionalization with amides as the coupling partners via selective activation of the amide N-C bond using rhodium(I) catalysts under highly chemoselective conditions is reported. Notably, this report constitutes the first catalytic activation of the amide N-C(O) bond by rhodium. We expect that this concept will have broad implications for using amides as coupling partners for C-H activation beyond the work described herein. (Figure Presented).
- Meng, Guangrong,Szostak, Michal
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p. 796 - 799
(2016/03/01)
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- Iridium(III)-Catalyzed Direct Arylation of C-H Bonds with Diaryliodonium Salts
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By developing a new Ir(III)-catalyzed C-C cross-coupling, a versatile method for direct arylation of sp2 and sp3 C-H bonds in ketoximes, nitrogen-containing heterocycles, various arenes, and olefins has been established. The key to this arylation depends on the appropriate choice of catalyst and the use of diaryliodonium triflate salts as the coupling partners. This transformation has good functional group compatibility and can serve as a powerful synthetic tool for late-stage C-H arylation of complex compounds. Mechanistic studies by density functional theory calculations suggested that the sp3 C-H activation was realized by a triflate-involved concerted metalation-deprotonation process, and the following oxidation of Ir(III) to Ir(V) is the most favorable when a bistriflimide is contained in the diaryliodonium salt. Calculations indicated that both steps are enabled by initial anion exchange between the reactant complexes.
- Gao, Pan,Guo, Wei,Xue, Jingjing,Zhao, Yue,Yuan, Yu,Xia, Yuanzhi,Shi, Zhuangzhi
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supporting information
p. 12231 - 12240
(2015/10/12)
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- Cobalt-catalyzed C-H bond functionalizations with aryl and alkyl chlorides
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Inexpensive cobalt catalysts derived from N-heterocylic carbenes (NHC) allowed efficient catalytic C-H bond arylations on heteroaryl-substituted arenes with widely available aryl chlorides, which set the stage for the preparation of sterically hindered tr
- Punji, Benudhar,Song, Weifeng,Shevchenko, Grigory A.,Ackermann, Lutz
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supporting information
p. 10605 - 10610
(2013/08/23)
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- Rhodium-catalyzed cross-coupling reactions of carboxylate and organoboron compounds via chelation-assisted C-C bond activation
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A new rhodium-catalyzed decarbonylated coupling reaction of ethyl benzo[h]quinoline-10-carboxylate and organoboron compounds that occurs through chelation-assisted sp2 C-COOEt bond activation was described. In this system CuCl played a very important role, and a five-membered rhodacycle was also involved as a key intermediate. Various functionalities were compatible in the reaction, and the desired products were obtained in good to excellent yields. DFT calculations on the mechanisms of this reaction using a Rh(I) model catalyst have also been carried out.
- Wang, Jingjing,Liu, Bowen,Zhao, Haitao,Wang, Jianhui
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p. 8598 - 8607
(2013/02/23)
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- Iron-catalyzed nitrogen-directed coupling of arene and aryl bromides mediated by metallic magnesium
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2-Arylpyridines, 2-alkenylpyridine, and aromatic imines can be coupled with aryl bromides in the presence of an iron catalyst, metallic magnesium, a diamine ligand and an organic dihalide oxidant at 0 °C. The use of a 1:1 mixture of tetrahydrofuran and 1,
- Ilies, Laurean,Kobayashi, Motoaki,Matsumoto, Arimasa,Yoshikai, Naohiko,Nakamura, Eiichi
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supporting information; experimental part
p. 593 - 596
(2012/04/23)
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- Direct cross-coupling of C-H bonds with grignard reagents through cobalt catalysis
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Go go Grignard! The first highly regioselective, cobalt-catalyzed C-H transformation of benzo[h]quinoline and phenylpyridine derivatives with Grignard reagents at room temperature has been achieved (see scheme). Both aryl and alkyl Grignard reagents showed significant reactivity.
- Li, Bin,Wu, Zhen-Hua,Gu, Yi-Fan,Sun, Chang-Liang,Wang, Bai-Quan,Shi, Zhang-Jie
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supporting information; experimental part
p. 1109 - 1113
(2011/04/22)
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- RuCi3 xH2O-catalyzed direct arylation of arenes with aryl chlorides in the presence of triphenylphosphine
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A study was conducted to demonstrate the RuCl3·xH 2O catalytic system for direct arylation of arenes with aryl chlorides. The phenylation of benzo[h]quinoline with chlorobenzene was investigated under preliminary studies. The reaction of benzo[h]quinoline and chlorobenzene N-methyl-2-pyrrolidone (NMP) formed Ph as the only product in 86-93% yields at 120-130 8C in the presence of K2CO3 using 5 mol% RuCl3·xH2O and 10 mol% PPh3. It was observed that the presence of an excess of ligand did not affect formation of Ph, while sub-stoichiometric ligand amounts led to a reduced conversion for benzo[h]quinoline. The arylation and benzylation of benzo[h]quinoline with various aryl chlorides was also investigated under the study.
- Luo, Ning,Yu, Zhengkun
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supporting information; experimental part
p. 787 - 791
(2010/05/19)
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- (η6-arene)ruthenium(N-heterocyclic carbene) complexes for the chelation-assisted arylation and deuteration of arylpyridines: Catalytic studies and mechanistic insights
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A series of (η6-arene)ruthenium complexes have been tested in the arylation of arylpyridines. One (η6-p-cymene)ruthenium(N- heterocyclic carbene) complex (labelled as 1 in the text) was found to be the most effective, being capable of arylating a wide set of substantially different arylpyridines. Complex 1 is also able to promote the regioselective deuteration of a series of arylated N-heterocycles, via a nitrogen-directed mechanism. Two of the deuterated amines were used to measure the kinetic isotope effect (KIE) in the arylation process. The detection of an inverse KIE, together with the observation that the C-H activation process does not require the addition of a base, suggest that the rate-limiting step in the arylation process may be different to that of previously reported studies.
- Prades, Amparo,Poyatos, Macarena,Peris, Eduardo
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experimental part
p. 1155 - 1162
(2010/07/03)
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- Efficient Rh(I)-Catalyzed direct arylation and alkenylation of arene C-H bonds via decarbonylation of benzoic and cinnamic anhydrides
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Efficient rhodium(I)-catalyzed regioselective direct arylation and alkenylation of aromatic C-H bonds has been realized with aromatic carboxylic and cinnamic anhydrides as the coupling partners via decarbonylation and C-H activation under phosphine-free c
- Jin, Weiwei,Yu, Zhengkun,He, Wei,Ye, Wenjing,Xiao, Wen-Jing
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scheme or table
p. 1317 - 1320
(2009/10/02)
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- Rhodium-catalyzed regioselective C-H functionalization via decarbonylation of acid chlorides and C-H bond activation under phosphine-free conditions
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Efficient rhodium(I)-catalyzed regioselective functionalization of aromatic C-H bonds has been realized with acid chlorides as the coupling partners via decarbonylation and C-H activation under phosphine-free conditions. Copyright
- Zhao, Xiaodan,Yu, Zhengkun
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supporting information; body text
p. 8136 - 8137
(2009/02/02)
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