- New air-stable planar chiral ferrocenyl monophosphine ligands: Suzuki cross-coupling of aryl chlorides and bromides
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(Matrix presented) A novel class of planar chiral electron-rich monophosphine ligands has been developed. The modular design allows a short and efficient synthesis of an array of aryl-ferrocenyl derivatives carrying the donating bis(dicyclohexyl)phosphino moiety. These new ligands have successfully been applied in the palladium-catalyzed Suzuki cross-coupling of activated as well as nonactivated aryl chlorides at room temperature. The asymmetric coupling of an aryl bromide and an aryl boronic acid was also tested, giving ees up to 54%.
- Jensen, Jakob F.,Johannsen, Mogens
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- Cu-Catalyzed Denitrogenative Ring-Opening of 3-Aminoindazoles for the Synthesis of Aromatic Nitrile-Containing (Hetero)Arenes
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An unprecedented Cu-catalyzed oxidative cleavage of two C-N bonds of 3-aminoindazoles is reported herein, which represents the first example for denitrogenative ring-opening of 3-aminoindazoles. This novel reactivity of 3-aminoindazoles enables the produc
- Zhou, Yao,Deng, Shuilin,Mai, Shaoyu,Song, Qiuling
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supporting information
p. 6161 - 6165
(2018/10/05)
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- The Rational Design and Synthesis of Water-Soluble Thiourea Ligands for Recoverable Pd-Catalyzed Aerobic Aqueous Suzuki-Miyaura Reactions at Room Temperature
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Eight precatalysts containing carboxylic-functionalized thiourea ligands are prepared and their activities and recyclability are evaluated in aerobic aqueous Suzuki-Miyaura reactions. A bulky monothiourea-Pd complex, functionalized with four carboxylic groups, shows the best activity and recyclability in the coupling of aryl bromides with arylboronic acids. The catalyst can be reused at least five times without any significant reduction in its catalytic activity. TEM analysis and the confirmed catalytic activity of the observed black precipitate reveal that Pd nanoparticles are formed during the reactions and are stabilized by the carboxylic-functionalized thiourea ligands.
- Chen, Wei,Lu, Xiao-Yan,Xu, Bei-Hua,Yu, Wei-Guo,Zhou, Zi-Niu,Hu, Ying
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p. 1499 - 1510
(2018/01/17)
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- A simple and mild Suzuki reaction protocol using triethylamine as base and solvent
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A simple and mild protocol for the palladium-catalyzed Suzuki reaction of aryl bromides and arylboronic acids is developed. The cross-coupling reactions can be performed at room temperature using 5.0 equiv. of Et3N as solvent and base without any ligands, and affording biaryl products in good yields. In addition, the chemoselecitive Suzuki reaction of bromo-N-methyliminodiacetic acid (MIDA) boronates with arylboronic acids can be achieved in this system, and various unsymmetrical terphenyls have been prepared in moderate yields by one-pot double Suzuki reactions.
- Li, Xinmin,Zhang, Hang,Hu, Qinghong,Jiang, Bo,Zeli, Yuan
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supporting information
p. 3123 - 3132
(2018/12/04)
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- Ruthenium-catalyzed hydrogenation of carbocyclic aromatic amines: Access to chiral exocyclic amines
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The first highly enantioselective hydrogenation of carbocyclic aromatic amines has been successfully realized using in situ-generated chiral ruthenium complex as catalyst, affording facile access to chiral exocyclic amines with up to 98% ee.
- Yan, Zhong,Xie, Huan-Ping,Shen, Hong-Qiang,Zhou, Yong-Gui
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supporting information
p. 1094 - 1097
(2018/02/23)
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- An N-Heterocyclic Carbene-Nickel Half-Sandwich Complex as a Precatalyst for Suzuki-Miyaura Coupling of Aryl/Heteroaryl Halides with Aryl/Heteroarylboronic Acids
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A nickel half-sandwich complex supported by our original NHC ligand was developed as a robust precatalyst for Suzuki-Miyaura cross-coupling. The addition of PPh3 was a crucial element in the suppression of side reactions and in accelerating the cross-coupling reaction. By employing the optimal conditions, aryl-aryl, heteroaryl-aryl, and heteroaryl-heteroaryl couplings were achieved.
- Ando, Shin,Matsunaga, Hirofumi,Ishizuka, Tadao
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p. 1266 - 1272
(2018/06/18)
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- Palladium-catalyzed ligand-free and efficient Suzuki-Miyaura reaction of N-methyliminodiacetic acid boronates in water
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A green and efficient protocol has been developed for the Pd(OAc)2-catalyzed ligand-free Suzuki-Miyaura reaction of N-methyliminodiacetic acid (MIDA) boronates in water. In the presence of Pd(OAc)2 as a catalyst and (i-Pr)2NH as a base, the cross-coupling reactions of aryl bromides with aryl MIDA boronates proceeded smoothly in water without any surfactant, and various functional groups were tolerated under the optimized conditions.
- Liu, Chun,Li, Xinmin,Wang, Xinnan,Qiu, Jieshan
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p. 1208 - 1215
(2016/03/01)
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- In situ-generated nano-palladium-catalyzed ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates at room temperature
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A mild and simple protocol is described for the palladium-catalyzed ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates in aqueous ethanol at room temperature. Palladium nanoparticles are generated in situ in the reaction and demonstrate high activity towards a wide range of aryl bromides and potassium aryltrifluoroborates, providing biphenyls in good to excellent yields. Interestingly, only 1 equiv of K2CO3 is used in this catalytic system. Moreover, the key biaryl intermediate of 2-cyano-4′-methylbiphenyl within valsartan is prepared in a 95% yield after 2 h.
- Liu, Chun,Li, Xinmin,Gao, Zhanming,Wang, Xinnan,Jin, Zilin
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supporting information
p. 3954 - 3959
(2015/06/02)
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- Water-soluble salen-Pd complex as an efficient catalyst for Suzuki-Miyaura reaction of sterically hindered substrates in pure water
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Water-soluble 2N2O-salen ligands and their palladium complexes were synthesized and used as efficient catalysts for the Suzuki-Miyaura reactions in pure water. Notably, the reactions of substrates with sterically demanding ortho substituents (aryl bromides and/or arylboronic acids) proceed smoothly to generate corresponding products with moderate to high yields using 0.5 mol % (salph)Pd (salph=N,N′-bis(4-SO3Na-salicylidene)-1,2-phenylenediamine) as the catalyst. Importantly, the catalytic system has the wide substrate scope and the high tolerance to various functional groups, including cyano, amino, nitro, methoxy, and acetyl. Moreover, the biaryl compounds were also obtained on a multi-gram scale by simple recrystallization with the system in the absence of any organic solvent, surfactant, or phase transfer agent and the catalyst was reused directly for the next cycle. Particularly, this protocol can be applied to synthesize aryl-substituted carbazolyl compounds.
- Liu, Ya-Shuai,Gu, Ning-Ning,Liu, Ping,Ma, Xiao-Wei,Liu, Yan,Xie, Jian-Wei,Dai, Bin
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supporting information
p. 7985 - 7989
(2015/12/31)
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- Zwitterionic palladium complexes: Room-temperature Suzuki-Miyaura cross-coupling of sterically hindered substrates in an aqueous medium
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A series of new imidazolium chlorides were straightforwardly prepared from the reactions between chloroacetone and imidazole derivatives. Deprotonation of the methylene proton next to the ketone group in these salts by pyridine led to the formation of a monodentate ligand that coordinated to palladium, readily forming zwitterionic anionic palladium pyridine complexes bearing a formal positive charge on the ligand ancillary. The pyridine ligand in the zwitterionic complexes can be facilely replaced by phosphine ligands. Seven of these new complexes were successfully characterized by X-ray crystallography. The zwitterionic phosphine complexes were highly efficient in catalyzing room-temperature Suzuki-Miyaura reactions between sterically hindered aryl chlorides and arylboronic acids in an aqueous medium.
- Lee, Jhen-Yi,Ghosh, Dabalina,Lee, Jing-Yi,Wu, Shih-Sheng,Hu, Ching-Han,Liu, Shuang-De,Lee, Hon Man
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p. 6481 - 6492
(2015/02/19)
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- Novel N-biphenyl-2-ylmethyl 2-methoxyphenylpiperazinylalkanamides as 5-HT7R antagonists for the treatment of depression
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5-HT7 receptor (5-HT7R) is a promising target for the treatment of depression and neuropathic pain. 5-HT7R antagonists exhibited antidepressant effects, while the agonists produced strong anti-hyperalgesic effects. In our efforts to discover selective 5-HT 7R antagonists or agonists, N-biphenylylmethyl 2- methoxyphenylpiperazinylalkanamides 1 were designed, synthesized, and biologically evaluated against 5-HT7R. Among the synthesized compounds, N-2′-chlorobiphenylylmethyl 2- methoxyphenylpiperazinylpentanamide 1-8 showed the best binding affinity with a Ki value of 8.69 nM and it was verified as a novel antagonist according to functional assays. The compound 1-8 was very selective over 5-HT1DR, 5-HT2AR, 5-HT3R, 5-HT5AR and 5-HT6R and moderately selective over 5-HT1AR, 5-HT1BR and 5-HT2CR. The novel 5-HT7R antagonist 1-8 exhibited an antidepressant effect at a dose of 25 mg/kg in the forced swimming test in mice and showed a U-shaped dose-response curve which typically appears in 5-HT7R antagonists such as SB-269970 and lurasidone.
- Kim, Youngjae,Tae, Jinsung,Lee, Kangho,Rhim, Hyewhon,Choo, Il Han,Cho, Heeyeong,Park, Woo-Kyu,Keum, Gyochang,Choo, Hyunah
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p. 4587 - 4596
(2014/10/15)
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- Pd/C-catalyzed ligand-free and aerobic Suzuki reaction in water
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A general and efficient catalytic system for Pd/C-catalyzed ligand-free aerobic Suzuki cross-coupling reactions was developed. The reaction tolerated a wide range of aryl bromides with a hydrophilic group or a hydrophobic group without any additives in water. Moreover, the catalytic system was successfully extended to the cross-couplings of heteroaryl halides with various arylboronic acids. The Pd/C catalyst could be reuse three times without significant loss of catalytic activity.
- Rao, Xiaofeng,Liu, Chun,Zhang, Yixia,Gao, Zhanming,Jin, Zilin
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p. 357 - 361
(2014/04/03)
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- Synthesis, characterization and catalytic activity of palladium complexes with α-imino-amidos ligands
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In the present work, a series of steric substituted α-imino-amido palladium complexes, {[Ar-NC(CH3)-C(CH3)(R)-NH-Ar] PdCl2} (C1, R = Me, Ar = 2,6-dimethylphenyl; C2, R = Me, Ar = 2,6-diisopropylphenyl; C3, R = CH2Ph, Ar = 2,6-dimethylphenyl; C4, R = CH2Ph, Ar = 2,6-diisopropylphenyl), were synthesized and characterized. The structures of palladium complexes C3 and C4 were elucidated by X-ray diffraction. These bidentate nitrogen ligands were applied in palladium-catalyzed Suzuki-Miyaura cross-coupling reactions. The effect of ligand substitution as well as reaction conditions on catalytic activity was evaluated. Under the optimization process, the less bulky and electron-donating ligand were successfully used to catalyze the reaction of a variety of aryl bromides and chlorides with arylboronic acids, giving the desired biaryl products in high yields.
- Cao, Gao,Yang, Hai-Qing,Luo, Bao-Tian,Liu, Feng-Shou
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p. 158 - 165
(2013/10/01)
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- Novel syntheses of fluorenones via nitrile-directed palladium-catalyzed C-H and dual C-H bond activation
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Novel procedures for the [Pd]/[Ag]/TFA system catalyzed cascade reactions of nitrile directed remote C-H and dual C-H bond activation with insertion of nitrile were developed, which afforded variously polysubstituted fluorenones in moderate to good yields with tolerance of a wide variety of substrates.
- Wan, Jung-Chih,Huang, Jun-Min,Jhan, Yu-Huei,Hsieh, Jen-Chieh
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supporting information
p. 2742 - 2745
(2013/07/19)
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- Palladium-catalyzed desulfitative arylation by C-O bond cleavage of aryl triflates with sodium arylsulfinates
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An efficient Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates as arylation reagents by C-O bond cleavage of aryl triflates was developed. With only 2 mol % of Pd(OAc)2 as catalyst and XPhos as ligand, the reaction proceeded well for a range of substrates.
- Zhou, Chao,Liu, Qingjiang,Li, Yaming,Zhang, Rong,Fu, Xinmei,Duan, Chunying
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p. 10468 - 10472
(2013/01/15)
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- Synthesis of biaryls through a one-pot tandem borylation/Suzuki-Miyaura cross-coupling reaction catalyzed by a palladacycle
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The tricyclohexylphosphane adduct of cyclopalladated ferrocenylimine I exhibited high catalytic activity in the one-pot borylation/Suzuki-Miyaura coupling (BSC) reaction with low catalyst loading (2 mol-%). Various biaryls were obtained in good to excellent yields for 37 examples. This process was applied to aryl and heteroaryl halides (Br and Cl) containing a variety of functional groups and did not require an excess amount of phosphane ligand and the addition of the palladium catalyst in the second step. Cyclopalladated ferrocenylimine I exhibited high catalytic activity in the borylation/Suzuki- Miyaura coupling (BSC) reaction with low catalyst loading. Various unsymmetrical biaryls were obtained ingood to excellent yields in one pot. This protocol was applied to aryl and heteroaryl halides (Br and Cl) containing a variety of functional groups without adding catalyst in the second step. Copyright
- Wang, Lianhui,Cui, Xiuling,Li, Jingya,Wu, Yusheng,Zhu, Zhiwu,Wu, Yangjie
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experimental part
p. 595 - 603
(2012/03/09)
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- Copper-catalyzed aerobic spirocyclization of biaryl-N-H-imines via 1,4-aminooxygenation of benzene rings
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A synthetic method of azaspirocyclohexadienones has been developed through copper-catalyzed aerobic spirocyclization of biaryl-N-H-imines prepared by the reaction of biarylcarbonitriles and Grignard reagents.
- Tnay, Ya Lin,Chen, Cheng,Chua, Yi Yuan,Zhang, Line,Chiba, Shunsuke
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supporting information; experimental part
p. 3550 - 3553
(2012/07/30)
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- A simple and efficient approach for the palladium-catalyzed ligand-free Suzuki reaction in water
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A general and efficient protocol is described for the palladium-catalyzed ligand-free and aerobic Suzuki reaction in water in the absence of any additive. The results demonstrate that the base played a crucial role in the high efficiency. The Pd(OAc)2/(i-Pr)2NH/H2O system showed the highest catalytic activity towards the Suzuki reaction of a wide range of aryl halides bearing hydrophilic or hydrophobic groups.
- Liu, Chun,Zhang, Yixia,Liu, Ning,Qiu, Jieshan
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supporting information
p. 2999 - 3003,5
(2020/09/16)
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- A convenient synthesis of benzonitriles via electrophilic cyanation with N-cyanobenzimidazole
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(Chemical Equation Presented) Couplings: N-Cyanobenzimidazole has been used in the synthesis of aryl- and heteroarylnitriles from the corresponding Grignard reagents (see scheme). This electrophilic cyanation is further extended to the synthesis of 2-cyano1,1'-biaryls through a domino Grignard-coupling/ cyanation strategy.
- Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 4725 - 4728
(2010/07/04)
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- N-heterocyclic benzhydrylamines as new N,N-bidentate ligands in palladium complexes: Synthesis, characterization and catalytic activity
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The synthesis of new N,N-bidentate ligands based on a π-deficient N-heterocyclic benzhydrylamine core is described. The corresponding air-stable palladium complexes are obtained in high yields and fully characterized by NMR spectroscopy and X-ray structur
- Terrasson, Vincent,Prim, Damien,Marrot, Jerome
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scheme or table
p. 2739 - 2745
(2009/03/12)
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- First cross-coupling reaction of potassium aryltrifluoroborates with organic chlorides in aqueous media catalyzed by an oxime-derived palladacycle
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(Chemical Equation Presented) Potassium aryltrifluoroborates are cross-coupled with aryl and heteroaryl chlorides using a 4-hydroxyacetophenone oxime-derived palladacycle as precatalyst, K2CO3 as base, and TBAB as additive in refluxing water under conventional and microwave heating affording the corresponding biphenyls under phosphine-free conditions. For the arylation of allyl and benzyl chlorides, KOH is used as base in acetone-water (3:2) at rt or 50 °C using 0.1 mol % Pd loading providing allylbenzenes and diarylmethanes, respectively.
- Alacid, Emilio,Najera, Carmen
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supporting information; scheme or table
p. 5011 - 5014
(2009/05/31)
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- Efficient Negishi coupling reactions of aryl chlorides catalyzed by binuclear and mononuclear nickel-N-heterocyclic carbene complexes
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(Chemical Equation Presented) We describe the first nickel-N-heterocyclic carbene catalyzed Negishi cross-coupling reaction of a variety of unactivated aryl chlorides, heterocyclic chlorides, aryl dichlorides, and vinyl chloride. The mononuclear and binuclear nickel-NHC complexes supported by heteroarene-functionalized NHC ligands are found to be highly efficient for the coupling of unactivated aryl chlorides and organozinc reagents, leading to biaryls and terphenyls in good to excellent yields under mild conditions. For all aryl chlorides, the binuclear nickel catalysts show activities higher than those of mononuclear nickel complexes because of possible bimetallic cooperative effect.
- Xi, Zhenxing,Zhou, Yongbo,Chen, Wanzhi
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experimental part
p. 8497 - 8501
(2009/04/04)
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- Synthesis, structural, and electron topographical analyses of a dialkylbiaryl phosphine/arene-ligated palladium(I) dimer: Enhanced reactivity in Suzuki-Miyaura coupling reactions
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The treatment of bis(2-(dicyclohexylphosphino)-2′,6′- dimethoxybiphenyl)PdCl2 with AgBF4 produces an air-stable phosphine/arene-ligated Pd(I) dimer with two seemingly identical Pd-arene interactions by X-ray crystallography. However, NMR and theoretical electron topographical analyses of this complex distinguish between these two interactions. One interaction is classified as an arenium-like complex, while the other is classified as a π-interaction. Additionally, this complex is a suitable precatalyst for high yielding Suzuki-Miyaura coupling reactions in short reaction times.
- Barder, Timothy E.
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p. 898 - 904
(2007/10/03)
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- Palladium catalyzed Suzuki-Miyaura coupling with aryl chlorides using a bulky phenanthryl N-heterocyclic carbene ligand
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A novel bis-phenanthryl N-heterocyclic carbene (NHC) based palladium acetate catalyst was effective for the coupling of various aryl and vinyl chlorides with organoboron compounds. N,N-Bis-(2,9-dicyclohexyl-10-phenanthryl)- 4,5-dihydroimidazolium chloride 8 (H2ICP·HCl) with Pd(OAc)2 and KF·18-c-6 in THF at room temperature gave Suzuki-Miyaura coupling of aryl and vinyl chorides, including unactivated and di-ortho substituted substrates in high yields. Hindered tri- and tetra-ortho substituted products were also efficiently produced. Benzyl chloride was also found to be a useful coupling partner and trimethylboroxine was used to give methylated products. The effect of ligand, base, temperature, solvent, and reaction time are reported along with various substrates including halides and triflates.
- Song, Chun,Ma, Yudao,Chai, Qiang,Ma, Chanqin,Jiang, Wei,Andrus, Merritt B.
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p. 7438 - 7446
(2007/10/03)
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- Novel class of tertiary phosphine ligands based on a phospha-adamantane framework and use in the Suzuki cross-coupling reactions of aryl halides under mild conditions
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(Matrix presented). A new class of sterically hindered phosphines based on a phospha-adamantane framework is described. Arylation or alkylation of the 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phospha-adamantane system allows for the preparation of tertiary phosphines suitable for use in palladium-catalyzed cross-coupling reactions. For example, use of a catalytic system incorporating Pd2(dba)3 and 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6-phospha-adamantane is shown to promote the Suzuki cross-coupling of aryl iodides, bromides, and activated chlorides with a variety of aryl boronic acids at room temperature in a few hours with high yields.
- Adjabeng, George,Brenstrum, Tim,Wilson, Jeffrey,Frampton, Christopher,Robertson, Al,Hillhouse, John,McNulty, James,Capretta, Alfredo
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p. 953 - 955
(2007/10/03)
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- A surprisingly mild and versatile method for palladium-catalyzed Suzuki cross-couplings of aryl chlorides in the presence of a triarylphosphine
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In the presence of new air-stable triarylphosphine 2, palladium-catalyzed Suzuki reactions of a wide array of aryl chlorides can be accomplished in uniformly good yield, including couplings of very sterically demanding and electronically deactivated subst
- Liu,Choi,Fu
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p. 2408 - 2409
(2007/10/03)
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- Preparation of unsymmetrical biaryls via palladium-catalyzed coupling reaction of aryl halides
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The synthesis of unsymmetrical biaryls is achieved using Pd(OAc)2 as the catalyst. A great variety of aryl halides having electron withdrawing and electron donating functional groups in para, meta and ortho positions have been successfully coupled.
- Hassan, Jwanro,Hathroubi, Chokri,Gozzi, Christel,Lemaire, Marc
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p. 7845 - 7855
(2007/10/03)
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- Versatile palladium-catalyzed arylation of organomanganese chlorides by aryl bromides
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In THF, a palladium-catalyzed cross-coupling reaction of organomanganese reagents with various aryl bromides including unreactive deactivated or hindered aryl bromides was performed successfully in the presence of a new catalytic system 1% PdCl2(dppp)-four equivalents DME. The scope of the reaction is very broad since many functional groups are tolerated, moreover, even hindered O,O′-di- or trisubstituted diaryls were obtained in high yields. It is interesting to note that hindered aryl bromides are more reactive than the corresponding aryl iodides. Alkyl, alkenyl and alkynylmanganese chlorides also react under similar conditions.
- Riguet, Eric,Alami, Mouad,Cahiez, Gérard
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p. 376 - 379
(2007/10/03)
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