- N-Heterocyclic Carbene Palladium(II) Amine Complexes: The Role of Primary Aryl- or Alkylamine Binding and Applications in the Buchwald-Hartwig Amination Reaction
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N-heterocyclic carbene-palladium(II) amine complexes bearing primary aryl- or alkylamines were synthesized. The prepared complexes were characterized by single crystal X-ray diffraction as well as NMR spectroscopy. These complexes exhibited good catalytic activities for the Buchwald-Hartwig amination reaction of aryl chlorides to afford arylated anilines under mild conditions. All reactions were carried out in air and all starting materials were used as supplied without purification. 21 expected coupling products were obtained in moderate to high yields under optimum conditions.
- Hsu, Yu-Cheng,Chen, Ming-Tsz
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supporting information
(2021/12/24)
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- L-Proline N-oxide dihydrazides as an efficient ligand for cross-coupling reactions of aryl iodides and bromides with amines and phenols
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A novel catalytic system based on L-proline N-oxide/CuI was developed and applied to the cross-coupling reactions of various N- and O- nucleophilic reagents with aryl iodides and bromides. This strategy featured in the employment of an-proline derived dihydrazides N-oxide compound as the superior supporting ligand. By using this protocol, a variety of products, including N-arylimidazoles, N-arylpyrazoles, N-arylpyrroles, N-arylamines, and aryl ethers, were synthesized with up to 99% yield.
- Ding, Zhiqiang,Nie, Nan,Chen, Tian,Meng, Lingxin,Wang, Gongshu,Chen, Zhangpei,Hu, Jianshe
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supporting information
(2020/12/21)
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- An Improved PIII/PV=O-Catalyzed Reductive C-N Coupling of Nitroaromatics and Boronic Acids by Mechanistic Differentiation of Rate- And Product-Determining Steps
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Experimental, spectroscopic, and computational studies are reported that provide an evidence-based mechanistic description of an intermolecular reductive C-N coupling of nitroarenes and arylboronic acids catalyzed by a redox-active main-group catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide, i.e., 1·[O]). The central observations include the following: (1) catalytic reduction of 1·[O] to PIII phosphetane 1 is kinetically fast under conditions of catalysis; (2) phosphetane 1 represents the catalytic resting state as observed by 31P NMR spectroscopy; (3) there are no long-lived nitroarene partial-reduction intermediates observable by 15N NMR spectroscopy; (4) the reaction is sensitive to solvent dielectric, performing best in moderately polar solvents (viz. cyclopentylmethyl ether); and (5) the reaction is largely insensitive with respect to common hydrosilane reductants. On the basis of the foregoing studies, new modified catalytic conditions are described that expand the reaction scope and provide for mild temperatures (T ≥ 60 °C), low catalyst loadings (≥2 mol%), and innocuous terminal reductants (polymethylhydrosiloxane). DFT calculations define a two-stage deoxygenation sequence for the reductive C-N coupling. The initial deoxygenation involves a rate-determining step that consists of a (3+1) cheletropic addition between the nitroarene substrate and phosphetane 1; energy decomposition techniques highlight the biphilic character of the phosphetane in this step. Although kinetically invisible, the second deoxygenation stage is implicated as the critical C-N product-forming event, in which a postulated oxazaphosphirane intermediate is diverted from arylnitrene dissociation toward heterolytic ring opening with the arylboronic acid; the resulting dipolar intermediate evolves by antiperiplanar 1,2-migration of the organoboron residue to nitrogen, resulting in displacement of 1·[O] and formation of the target C-N coupling product upon in situ hydrolysis. The method thus described constitutes a mechanistically well-defined and operationally robust main-group complement to the current workhorse transition-metal-based methods for catalytic intermolecular C-N coupling.
- Li, Gen,Nykaza, Trevor V.,Cooper, Julian C.,Ramirez, Antonio,Luzung, Michael R.,Radosevich, Alexander T.
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supporting information
p. 6786 - 6799
(2020/04/30)
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- Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study
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Herein, we report a nickel-1,2-bis(dicyclohexylphosphino)ethane (dcype) complex for the catalytic Buchwald-Hartwig amination of aryl thioethers. The protocol shows broad applicability with a variety of different functional groups tolerated under the catalytic conditions. Extensive organometallic and kinetic studies support a nickel(0)-nickel(II) pathway for this transformation and revealed the oxidative addition complex as the resting state of the catalytic cycle. All the isolated intermediates have proven to be catalytically and kinetically competent catalysts for this transformation. The fleeting transmetalation intermediate has been successfully synthesized through an alternative synthetic organometallic pathway at lower temperature, allowing for in situ NMR study of the C-N bond reductive elimination step. This study addresses key factors governing the mechanism of the nickel-catalyzed Buchwald-Hartwig amination process, thus improving the understanding of this important class of reactions.
- Bismuto, Alessandro,Delcaillau, Tristan,Müller, Patrick,Morandi, Bill
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p. 4630 - 4639
(2020/05/19)
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- Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application
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Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.
- Sinai, ádám,Simkó, Dániel Cs.,Szabó, Fruzsina,Paczal, Attila,Gáti, Tamás,Bényei, Attila,Novák, Zoltán,Kotschy, András
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supporting information
p. 1122 - 1128
(2020/03/03)
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- Pyrazolyl bistriazolyl phosphine compound and application of pyrazolyl bistriazolyl phosphine compound
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The invention discloses a pyrazolyl bistriazolyl phosphine compound and application thereof. The invention discloses a compound shown as a formula I. In the formula I, R1 is hydrogen, C1-C6 alkyl or phenyl; R2 and R3 are phenyl; R4 and R5 are independently a C1-C6 alkyl group, a C3-C8 cycloalkyl group, or a phenyl group. The pyrazolyl bistriazolyl phosphine compound disclosed by the invention is stable in property, excellent in catalytic effect and high in selectivity, and can be applied to catalytic coupling of amine, boric acid compounds and halides.
- -
-
Paragraph 0219-0223
(2020/07/24)
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- Preparation method of pyrazole bistriazolylphosphine compound
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The invention discloses a preparation method of a pyrazole bistriazolylphosphine compound. The invention discloses a preparation method of a compound as shown in a formula I. The preparation method comprises the following step: under the action of an alkali, carrying out a phosphonation reaction process as shown in the specification on a compound as shown in a formula II and a compound as shown ina formula III in a solvent in the presence of protective gas to obtain the compound as shown in the formula I, wherein R1 is hydrogen, a C1-C6 alkyl group or a phenyl group, R2 and R3 are phenyl, R4and R5 are independently a C1-C6 alkyl group, a C3-C8 cycloalkyl group or a phenyl group and x is halogen. The pyrazolyl bistriazolylphosphine compound obtained by the preparation method disclosed bythe invention is stable in property, excellent in catalytic effect and high in selectivity, and can be applied to catalytic coupling of amine, boric acid compounds and halides.
- -
-
Paragraph 0217-0221
(2020/05/30)
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- Ullmann-type: N-arylation of anilines with alkyl(aryl)sulfonium salts
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A palladium/copper-cocatalyzed Ullmann-type N-arylation of anilines using alkyl(aryl)sulfonium triflates as arylation reagents has been accomplished. The reaction enabled Caryl-S bond cleavage over Calkyl-S bond breakage of alkyl(aryl)sulfoniums by Pd(P(tBu)3)2/CuI and gave the corresponding N-arylated products in good to high yields. It was also significant that the reactions of aniline with asymmetric butyl(mesityl)(aryl)sulfonium triflates showed excellent selectivity, in which the aryl groups other than the bulky and electron-rich mesityl moieties were transformed.
- Tian, Ze-Yu,Zhang, Cheng-Pan
-
supporting information
p. 11936 - 11939
(2019/10/11)
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- Palladium-catalyzed c(sp2)-n bond cross-coupling with triaryl phosphates
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The first general palladium-catalyzed amination of aryl phosphates is described. The combination of MorDalPhos with [Pd(-cinnamyl)Cl]2 enables the amination of electron-rich, electron-neutral, and electron-poor aryl phosphates with a board range of aromatic, aliphatic, and heterocyclic amines. Common functional groups such as ether, keto, ester, and nitrile show an excellent compatibility in this reaction condition. The solvent-free amination reactions are also successful in both solid coupling partners. The gram-scale cross-coupling is achieved by this catalytic system.
- Chen, Zicong,Chen, Xiangmeng,So, Chau Ming
-
-
- Palladium-Catalyzed C(sp2)-N Bond Cross-Coupling with Triaryl Phosphates
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The first general palladium-catalyzed amination of aryl phosphates is described. The combination of MorDalPhos with [Pd(?-cinnamyl)Cl]2 enables the amination of electron-rich, electron-neutral, and electron-poor aryl phosphates with a board range of aromatic, aliphatic, and heterocyclic amines. Common functional groups such as ether, keto, ester, and nitrile show an excellent compatibility in this reaction condition. The solvent-free amination reactions are also successful in both solid coupling partners. The gram-scale cross-coupling is achieved by this catalytic system.
- Chen, Zicong,Chen, Xiangmeng,So, Chau Ming
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p. 6366 - 6376
(2019/05/24)
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- Reductive Molybdenum-Catalyzed Direct Amination of Boronic Acids with Nitro Compounds
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The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C?N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. Moreover, this general and step-economical synthesis of aromatic secondary amines showcases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.
- Suárez-Pantiga, Samuel,Hernández-Ruiz, Raquel,Virumbrales, Cintia,Pedrosa, María R.,Sanz, Roberto
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supporting information
p. 2129 - 2133
(2019/01/25)
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- Nickel-catalyzed N-arylation of amines with arylboronic acids under open air
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In this study, a well-defined, novel NHC-Ni complex was developed and used to catalyze the N-arylation of alkyl- and arylamines with arylboronic acids in a rare version of Chan-Lam coupling. Although the same coupling using copper catalysts has been widely studied, the nickel-catalyzed version is rare and normally requires 10–20 mol% catalyst loading. This novel NHC-Ni complex in combination with 4,4′-dimethyl-2,2′-bipyridine, however, proved to be an effective catalyst that lowered the required catalyst loading to only 2.0 mol%.
- Ando, Shin,Hirota, Yurina,Matsunaga, Hirofumi,Ishizuka, Tadao
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supporting information
p. 1277 - 1280
(2019/04/10)
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- Palladium-catalyzed amination of aryl sulfoxides
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Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C-S bond amination reactions. This amination accommodated a wider range of functional groups such as silyl, boryl, methylsulfanyl, and halogen moieties. Regioselective amination of unsymmetrical diaryl sulfoxides was also executed by means of steric bias.
- Yoshida, Yuto,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 1134 - 1137
(2018/02/23)
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- Sulfonato-diketimine Copper(II) Complexes: Synthesis and Application as Catalysts in Chan-Evans-Lam Couplings
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Copper complexes bearing a diketimino-sulfonate ligand, LCu(NO3)(NCMe), were prepared and proved to be stable to water for several hours in solution. Prolonged standing in the presence of water or strong bases led to desulfonation of the ligand. LCu(NO3) was inactive in the polymerization of lactide (in the presence of benzyl alcohol), but showed high activity for the Chan-Evans-Lam coupling of a variety of amines and anilines. Couplings do not require addition of base, ligand, or molecular sieves. Mechanistic investigations indicate a catalytic cycle involving dioxygen as the required oxidant, precoordination of boronic acid to the sulfonate group, and transmetalation occurring prior to reaction with the nucleophile.
- Hardouin Duparc, Valérie,Schaper, Frank
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p. 3053 - 3060
(2017/09/05)
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- NI(0) CATALYSTS
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Provided herein are nickel(O) catalysts that are stable when exposed to air and can be used to catalyze the formation of a C-C, C-O, or C-N bond.
- -
-
Paragraph 0023; 0066
(2017/07/31)
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- Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald-Hartwig Amination in Air
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To achieve efficient palladium-catalyzed cross-coupling reaction under mild reaction conditions with the flexible steric bulk strategy, a series of Pd-PEPPSI (PEPPSI: pyridine-enhanced precatalyst preparation, stabilization, and initiation) complexes C1-C6 were synthesized and characterized, in which unsymmetric flexible steric bulk was introduced on the N-aryl of ancenaphthyl skeleton. These well-defined palladium complexes were found to be excellent precatalysts for Buchwald-Hartwig amination of aryl chlorides with amines in air. The electronic effect of the Pd-PEPPSI complexes and the effect of ancillary pyridine ligands were evaluated, among which complex C3 exhibited the most efficiency. It was demonstrated that the cross-coupling products were obtained in excellent yields in the presence of 0.5-0.1 mol % palladium loading. A wide range of aryl- and heteroaryl chlorides as well as various amines were compatible. The oxidative addition of aryl chlorides is revealed to be the rate-determining step in the catalytic cycle. The catalytic activity can be enhanced by introducing electron-donating groups to the Pd-PEPPSI complexes. This type of Pd-PEPPSI precatalyst showed the most efficiency reported to date for the challenging C-N cross-coupling reactions requiring no anhydrous and inert atmosphere protections, suggesting flexible steric bulk as a promising catalyst design strategy.
- Lan, Xiao-Bing,Li, Yinwu,Li, Yan-Fang,Shen, Dong-Sheng,Ke, Zhuofeng,Liu, Feng-Shou
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p. 2914 - 2925
(2017/03/23)
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- Water-soluble palladacycles containing hydroxymethyl groups: Synthesis, crystal structures and use as catalysts for amination and Suzuki coupling of reactions
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Two water-soluble monophosphine [PPh3 and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl(Sphos)]-palladacycles containing hydroxymethyl groups 2-3 were prepared by cyclopalladation and chloride bridge-splitting reactions. The complexes were characterized by elemental analysis, ESI-MS and NMR. In addition, single-crystal X-ray analysis reveals that they have one-dimensional lamellar structures involving intermolecular hydrogen bonds and π-π interactions. The use of these palladacycles as catalysts for amination and Suzuki coupling of aryl chlorides in water was investigated. Complex 3 was found to be very efficient for these coupling reactions. Additionally, it was also successfully used in Suzuki coupling of (hydroxymethyl)phenylboronic acid for the synthesis of substituted 2-N-heterocyclic biarylmethanols.
- Han, Xin,Li, Hong-Mei,Xu, Chen,Xiao, Zhi-Qiang,Wang, Zhi-Qiang,Fu, Wei-Jun,Hao, Xin-Qi,Song, Mao-Ping
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p. 403 - 411
(2016/04/19)
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- An easily available N-heterocyclic carbene–palladium(II) catalyst for Buchwald–Hartwig amination of aryl chlorides
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Abstract: An easily available N-heterocyclic carbene–palladium(II) complex was found to be an efficient catalyst for the Buchwald–Hartwig amination of aryl chlorides. Both secondary and primary amines were tolerated under the same reaction conditions. Under the optimal conditions, all reactions proceeded successfully to give the desired products in good to high yields within hours. Graphical Abstract: [Figure not available: see fulltext.]
- Wang, Tao,Xu, Kai,Liu, Lantao,Xie, Huanping,Li, Ying,Zhao, Wen-Xian
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p. 525 - 529
(2016/07/20)
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- Solvent-Free Buchwald-Hartwig (Hetero)arylation of Anilines, Diarylamines, and Dialkylamines Mediated by Expanded-Ring N-Heterocyclic Carbene Palladium Complexes
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A highly efficient solvent-free protocol for the Buchwald-Hartwig (hetero)arylation of anilines, diarylamines, and dialkylamines mediated by the expanded-ring N-heterocyclic carbene palladium complex (THP-Dipp)Pd(cinn)Cl [THP-Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; cinn = cinnamyl, 3-phenylallyl] was developed. The catalytic protocol was efficient for the coupling of amines and (hetero)aryl chlorides and bromides bearing donor, acceptor, and bulky substituents.
- Topchiy, Maxim A.,Dzhevakov, Pavel B.,Rubina, Margarita S.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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supporting information
p. 1908 - 1914
(2016/04/20)
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- Palladium-catalyzed amination of aryl sulfides with aliphatic amines
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Conditions for the palladium-NHC-catalyzed amination of aryl sulfides with aliphatic as well as aromatic amines were established. The KHMDS-mediated amination of heteroaryl sulfides could proceed without palladium. Based on the distinct difference in reactivity of C-Br and C-S bonds, a sequential amination of bromothioanisole can take place to install two different alkylamino groups onto the aromatic ring in one pot. A palladium-NHC precatalyst shows high efficiency for C-S bond cleavage for the amination of aryl sulfides with aliphatic amines or aromatic amines.
- Gao, Ke,Yorimitsu, Hideki,Osuka, Atsuhiro
-
supporting information
p. 2678 - 2682
(2015/04/27)
-
- An electroluminescent compound and an electroluminescent device comprising the same
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The present invention relates to an organic light emitting compound represented by chemical formula 1, and an organic electroluminescent device comprising the same. The organic light emitting compound according to the present invention increases PL quantu
- -
-
Paragraph 0216-0220
(2016/10/08)
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- Nickel-catalyzed amination of aryl chlorides and sulfamates in 2-methyl-THF
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The nickel-catalyzed amination of aryl O-sulfamates and chlorides using the green solvent 2-methyl-THF is reported. This methodology employs the commercially available and air-stable precatalyst NiCl2(DME), is broad in scope, and provides access to aryl amines in synthetically useful yields. The utility of this methodology is underscored by examples of gram-scale couplings conducted with catalyst loadings as low as 1 mol % nickel. Moreover, the nickel-catalyzed amination described is tolerant of heterocycles and should prove useful in the synthesis of pharmaceutical candidates and other heteroatom-containing compounds.
- Fine Nathel, Noah F.,Kim, Junyong,Hie, Liana,Jiang, Xingyu,Garg, Neil K.
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p. 3289 - 3293
(2015/02/19)
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- Facile synthesis of Fe@Pd nanowires and their catalytic activity in ligand-free CN bond formation in water
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This work reports a facile synthesis of Fe@Pd nanowires. Ligand-free cross coupling reactions of arylboronic acids with various amines in aqueous medium proceed in very good to excellent yield with the use of Fe@Pd nanowires. Furthermore, the catalyst could be easily separated from the reaction mixture using a magnet and could be recycled several times without loss of catalytic activity.
- Nasrollahzadeh, Mahmoud,Azarian, Abbas,Ehsani, Ali,Zahraei, Ali
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p. 2813 - 2817
(2014/05/06)
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- N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole complexes: Synthesis and catalytic activity toward amination of aryl chlorides
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A series of novel N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole (NHC-PdII-Ox) complexes 3 were successfully synthesized from commercially available imidazolium salts 1, PdCl2, and 4,5-dihydrooxazoles 2 in a one-step process, and these complexes showed efficient catalytic activity toward the amination of aryl chlorides. Both secondary and primary amines were tolerated under the same reaction conditions. Under the optimal reaction conditions, the expected coupling products were obtained in moderate to high yields.
- Huang, Pei,Wang, Yi-Xiang,Yu, Hong-Fei,Lu, Jian-Mei
-
supporting information
p. 1587 - 1593
(2014/05/06)
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- Formation of dispersed palladium-nickel bimetallic nanoparticles in microemulsions: Synthesis, characterization, and their use as efficient heterogeneous recyclable catalysts for the amination reactions of aryl chlorides under mild conditions
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A simple method for preparing spherical palladium-nickel bimetallic nanoparticles with a molar ratio of 1.0 (Pd0.5-Ni0.5 B-NPs) has been adopted using a water-in-oil microemulsion system of water/aerosol-OT/ isooctane at room temperature. The morphology, size, structure, and elemental composition of these particles as the superior catalyst were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive analysis using X-rays (EDAX), and X-ray fluorescence (XRF) analyses. The effects of the reaction parameters on the Buchwald-Hartwig amination reaction yield in the presence of these NPs as catalyst have been screened and the results are evaluated by using chlorobenzene and morpholine as a model reaction. Initially, differences in the catalytic properties of some synthesized NPs have been compared. In this context, Pd-Ni B-NPs with the molar ratio of 1 : 1 (Pd/Ni = 1) showed the highest catalytic activity for this reaction. The Pd0.5-Ni0.5 B-NPs are stable and the leaching of catalyst in solution is very low. Therefore, they has been employed as efficient catalysts in the C-N coupling reaction. Finally, a mechanism for an amination reaction on the Pd/Ni catalyst surface was proposed.
- Heshmatpour, Felora,Abazari, Reza
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p. 55815 - 55826
(2015/02/05)
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- Skeleton decoration of NHCs by amino groups and its sequential booster effect on the palladium-catalyzed Buchwald-Hartwig amination
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A challenging synthetic modification of PEPPSI-type palladium pre-catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald-Hartwig amination. This is illustrated, for example, by the quantitative amination of 4-chloroanisole by morpholine within 2 h at 25°C with a 2 mol% catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol%) for the coupling of aryl chlorides with anilines (max TON: 19600).
- Zhang, Yin,Cesar, Vincent,Storch, Golo,Lugan, Noel,Lavigne, Guy
-
supporting information
p. 6482 - 6486
(2014/06/24)
-
- The facet-dependent enhanced catalytic activity of Pd nanocrystals
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A systematic study of heterogeneous Buchwald-Hartwig amination using shape-controlled Pd nanocrystals with distinctly different surface facets is presented. This journal is the Partner Organisations 2014.
- Kim, Minjune,Kim, Yeonjoon,Hong, Jong Wook,Ahn, Seihwan,Kim, Woo Youn,Han, Sang Woo
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supporting information
p. 9454 - 9457
(2014/08/18)
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- Palladium-catalysed amination of aryl- and heteroaryl halides using tert-butyl tetraisopropylphosphorodiamidite as an easily accessible and air-stable ligand
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The phosphorus compound tert-butyl tetraisopropylphosphorodiamidite, prepared from bis(diisopropylamino)chlorophosphine, is an excellent ligand for palladium-catalysed Buchwald-Hartwig amination of aryl- and heteroaryl chlorides and bromides. Based on its ready accessibility and air-stability, this amination protocol is a practical approach to the synthesis of industrially important aryl- and heteroarylamines. Copyright
- Roiban, Gheorghe-Doru,Mehler, Gerlinde,Reetz, Manfred T.
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p. 2070 - 2076
(2014/04/17)
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- Solvent-free aryl amination catalysed by [Pd(NHC)] complexes
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A highly effective solvent-free protocol for the Buchwald-Hartwig amination of unactivated aryl chlorides is described. The effect of various [Pd(NHC)] pre-catalyst systems on the reactivity has been studied. [Pd(IPr*)(cin)Cl] is reported as the complex o
- Chartoire, Anthony,Boreux, Arnaud,Martin, Anthony R.,Nolan, Steven P.
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p. 3840 - 3843
(2013/04/23)
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- Novel robust benzimidazolylidene palladium complexes: Synthesis, structure, and catalytic applications in amination of chloroarenes
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A series of novel pyridine stabilized PdeNHC complexes were developed, which revealed high activities and broad substrates tolerance in the amination of various (hetero)-aryl chlorides. Besides various secondary amines, a wide range of primary anilines and aliphatic amines were also well tolerated. The results highlight us a new strategy to increase catalyst activity in the future catalyst design by alternating the σ-donor property and flexibility of NHC ligands.
- Fang, Weiwei,Jiang, Jian,Xu, Yong,Zhou, Juefei,Tu, Tao
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p. 673 - 679
(2013/07/27)
-
- AMINATION OF ARYL ALCOHOL DERIVATIVES
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Embodiments of the invention provide methods and materials for chemical cross-coupling reactions that utilize aryl alcohol derivatives as cross-coupling partners. Embodiments of the invention include methods for the amination of aryl sulfamates and carbamates, which are attractive cross-coupling partners, particularly for use in multistep synthesis. Illustrative embodiments include versatile means to use simple derivatives of phenol as precursors to polysubstituted aryl amines, as exemplified by a concise synthesis of the antibacterial drug linezolid.
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Page/Page column 47; 53
(2012/07/27)
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- Nickel-catalyzed amination of aryl sulfamates and carbamates using an air-stable precatalyst
-
A facile nickel-catalyzed method to achieve the amination of synthetically useful aryl sulfamates and carbamates is reported. Contrary to most Ni-catalyzed amination reactions, this user-friendly approach relies on an air-stable Ni(II) precatalyst, which, when employed with a mild reducing agent, efficiently delivers aminated products in good to excellent yields. The scope of the method is broad with respect to both coupling partners and includes heterocyclic substrates.
- Hie, Liana,Ramgren, Stephen D.,Mesganaw, Tehetena,Garg, Neil K.
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supporting information; experimental part
p. 4182 - 4185
(2012/09/25)
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- An efficient palladium-NHC (NHC=N-heterocyclic carbene) and aryl amination pre-catalyst: [Pd(IPr*)(cinnamyl)Cl]
-
The well-defined [Pd(IPr*)(cinnamyl)Cl] complex is reported as one of the best N-heterocyclic carbene (NHC)-based pre-catalysts for the Buchwald-Hartwig amination reaction. This catalytic system displays high efficiency for the coupling of numerous (heter
- Chartoire, Anthony,Frogneux, Xavier,Nolan, Steven P.
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experimental part
p. 1897 - 1901
(2012/09/25)
-
- Well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides
-
We report herein a well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides. Under the optimal reaction conditions, a variety of primary amines can be coupled with aryl chlorides to give the amination products in good to high yields within 4 h. It is worthy of noting here that the NHC-Pd(II)-Im complex showed especially high catalytic activity toward challenging sterically hindered substrates including both of aryl amines and aryl chlorides. In addition, alkyl amines were also proved to be suitable reaction partners to give the corresponding amination products in good to high yields.
- Zhu, Lei,Ye, Yue-Mei,Shao, Li-Xiong
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experimental part
p. 2414 - 2420
(2012/04/10)
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- Buchwald-Hartwig amination of aryl chlorides catalyzed by easily accessible benzimidazolyl phosphine-Pd complexes
-
This study describes the efficacy of benzimidazolyl phosphine ligands, which are easily synthesized from inexpensive and commercially available o-phenylenediamine, 2-bormobenzoic acid, and chlorophosphines, in the Buchwald-Hartwig amination of aryl chlorides. Primary and secondary aromatic/aliphatic amines are effective substrates in this catalytic system. Functional groups such as keto and esters are also compatible. The catalyst loading can be reduced to 0.1 mol% Pd. Georg Thieme Verlag Stuttgart · New York.
- Chung, Kin Ho,So, Chau Ming,Wong, Shun Man,Luk, Chi Him,Zhou, Zhongyuan,Lau, Chak Po,Kwong, Fuk Yee
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supporting information; experimental part
p. 1181 - 1186
(2012/06/15)
-
- A novel and efficient PEPPSI precatalyst
-
The preparation of the novel, well-defined [Pd(IPr*)(3-Cl-pyridinyl) Cl2] complex is described. The steric parameters of the ligand as well as its reactivity in the Buchwald-Hartwig amination were directly compared to other [Pd(NHC)(3-Cl-pyridi
- Chartoire, Anthony,Frogneux, Xavier,Boreux, Arnaud,Slawin, Alexandra M. Z.,Nolan, Steven P.
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p. 6947 - 6951
(2012/11/14)
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- N-Heterocyclic carbene adducts of cyclopalladated ferrocenylpyridine: Synthesis, structural characterization and reusable catalytic system for Suzuki and amination of aryl chlorides in poly(ethylene glycol-400)
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Two air-stable carbene adducts of cyclopalladated ferrocenylpyridine 1-2 have been synthesized and characterized by elemental analysis, IR, ESI-MS, 1H and 13C NMR. Additionally, their detailed structures have been determined by singl
- Xu, Chen,Li, Hong-Mei,Liu, Hu,Zhang, Zhi-Qiang,Wang, Zhi-Qiang,Fu, Wei-Jun,Zhang, Yu-Qing
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experimental part
p. 22 - 26
(2012/06/15)
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- Triphenylphosphine as a ligand for the Pd-catalyzed amination of unactivated aryl chlorides with anilines promoted by salicylaldimine
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An efficient and selective amination of unactivated aryl chlorides with anilines catalyzed by mixed ligand Pd catalytic system of Ph3P- salicylaldimine has been developed for the preparation of diarylamines. The benzyne mechanism was ruled out based on experimental results. Georg Thieme Verlag Stuttgart · New York.
- Liu, Tao-Ping,Cheng, Qiang,Song, Wen-Jing,Cai, Liang-Zhen,Tao, Xiao-Chun
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supporting information
p. 2333 - 2336
(2013/07/19)
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- Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride
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While pursuing the development of new hydroamination catalysts, a 3-iminophosphine palladium(II) chloride complex [(3IP)PdCl2] was synthesized that has subsequently proven to be an effective precatalyst for the aryl amination of bromoarenes. This (3IP)PdCl2 complex has been utilized in the catalytic aryl amination of both bromobenzene and bromopyridine derivatives, specifically yielding excellent activity in coupling reactions involving bromobenzene, 4-bromotoluene, and 2-bromopyridine. Using a standard set of catalytic conditions, many alkyl and aryl amines have been investigated as coupling partners in the aryl amination of bromoarenes. In general, secondary alkyl amines and ortho-substituted anilines proved to be the best substrates for this reaction, commonly giving quantitative conversion to products, while primary amines and other anilines gave only poor to moderate results. Catalytic screening data, product yields, and full characterization of isolated products are included.
- Samblanet, Danielle C.,Schmidt, Joseph A. R.
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p. 7 - 18,12
(2012/12/12)
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- Palladium-catalyzed monoarylation of aryl amine with aryl tosylates
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The bulky and electron-rich MOP-type ligand was efficient for the Pd-catalyzed amination of aryl tosylates. The in situ generated Pd(0) was a more efficient catalyst precursor than Pd(dba)2. In the presence of Pd(OAc)2, PhB(OH)2, and a hindered and electron-rich MOP-type ligand, a variety of primary aryl amines reacted with various aryl tosylates to form the corresponding secondary aryl amines in high yields with high selectivity. Furthermore, the catalyst system was also efficient for the arylation of indoles and hydrazones with aryl tosylates. Georg Thieme Verlag Stuttgart · New York.
- Xie, Xiaomin,Ni, Gang,Ma, Fangfang,Ding, Lina,Xu, Sheng,Zhang, Zhaoguo
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supporting information; experimental part
p. 955 - 958
(2011/06/17)
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- A highly efficient precatalyst for amination of aryl chlorides: Synthesis, structure and application of a robust acenaphthoimidazolylidene palladium complex
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A robust palladium NHC complex was synthesized and exhibits exceptional activity and selectivity as a precatalyst in the amination of aryl chlorides and tolerates a wide range of substrates at low catalyst loadings.
- Tu, Tao,Fang, Weiwei,Jiang, Jian
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supporting information; experimental part
p. 12358 - 12360
(2011/12/15)
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- Nickel-catalyzed amination of aryl sulfamates
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Broad in scope: The first amination of aryl sulfamates, which are attractive cross-coupling partners, particularly for multistep syntheses, was achieved by using a nickel catalyst. The method provides a versatile means to use simple derivatives of phenol as precursors to polysubstituted aryl amines, as exemplified by a concise synthesis of the antibacterial drug linezolid (see scheme).
- Ramgren, Stephen D.,Silberstein, Amanda L.,Yang, Yang,Garg, Neil K.
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p. 2171 - 2173
(2011/04/25)
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- Synthesis and X-ray structure determination of highly active Pd(II), Pd(I), and Pd(0) complexes of Di(tert -butyl)neopentylphosphine (DTBNpP) in the arylation of amines and ketones
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The air-stable complex Pd(eta;3-allyl)(DTBNpP)Cl (DTBNpP = di(tert-butyl)neopentylphosphine) serves as a highly efficient precatalyst for the arylation of amines and enolates using aryl bromides and chlorides under mild conditions with yields ranging from 74% to 98%. Amination reactions of aryl bromides were carried out using 1-2 mol % Pd(η3-allyl)(DTBNpP)Cl at 23-50 °C without the need to exclude oxygen or moisture. The C-N coupling of the aryl chlorides occurred at relatively lower temperature (80-100 °C) and catalyst loading (1 mol %) using the Pd(eta;3-allyl) (DTBNpP)Cl precatalyst than the catalyst generated in situ from DTBNpP and Pd2(dba)3 (100-140 °C, 2-5 mol % Pd). Other Pd(DTBNpP)2-based complexes, (Pd(DTBNpP)2 and Pd(DTBNpP)2Cl2) were ineffective precatalysts under identical conditions for the amination reactions. Both Pd(DTBNpP)2 and Pd(DTBNpP)2Cl2 precatalysts gave nearly quantitative conversions to the product in the α-arylation of propiophenone with p-chlorotoluene and p-bromoanisole at a substrate/catalyst loading of 100/1. At lower substrate/ca'alyst loading (1000/1), the conversions were lower but comparable to that of Pd(t-Bu3P)2. In many cases, the tri-tert-butylphosphine (TTBP) based Pd(I) dimer, [Pd(μ-Br)(TTBP)] 2, stood out to be the most reactive catalyst under identical conditions for the enolate arylation. Interestingly, the air-stable Pd(I) dimer, Pd2(DTBNpP)2(μ-Cl)(μ-allyl), was less active in comparison to [Pd(μ-Br)(TTBP)]2 and Pd(eta;3-allyl) (DTBNpP)Cl. The X-ray crystal structures of Pd(eta;3-allyl)(DTBNpP) Cl, Pd(DTBNpP)2Cl2, Pd(DTBNpP)2, and Pd 2(DTBNpP)2(μ-Cl)(μ-allyl) are reported in this paper along with initial studies on the catalyst activation of the Pd(eta;3-allyl)(DTBNpP)Cl precatalyst.
- Hill, Lensey L.,Crowell, Jason L.,Tutwiler, Strudwick L.,Massie, Nicholas L.,Hines, C. Corey,Griffin, Scott T.,Rogers, Robin D.,Shaughnessy, Kevin H.,Grasa, Gabriela A.,Johansson Seechurn, Carin C. C.,Li, Hongbo,Colacot, Thomas J.,Chou, Joe,Woltermann, Christopher J.
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supporting information; experimental part
p. 6477 - 6488
(2010/12/24)
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- Reactive 4a-alkyl-4aH-carbazoles by catalytic dearomatisation, and their unusual dimerisation and dealkylation reactions
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Despite their intrinsic instability, 4a-alkyl-4aH-carbazoles can be generated by a catalytic dearomatisation process; their reactivity is demonstrated by facile dealkylation and highly unusual cyclodimerisation processes.
- Bedford, Robin B.,Butts, Craig P.,Haddow, Mairi F.,Osborne, Robert,Sankey, Rosalind F.
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scheme or table
p. 4832 - 4834
(2009/12/08)
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- Pentavalent organoantimony compounds as mild N-arylating agents for amines: Cu-mediated ullmann-type N-arylation with tetraarylantimony(V) acetates
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Simple and mild Cu-mediated arylation of various amines by use of tetraarylantimony acetate (Ar4SbOAc) is described. The Ullmann-type condensation of Ar4SbOAc with aliphatic and electron rich aromatic amines proceeded efficiently in
- Qin, Weiwei,Kakusawa, Naoki,Wu, Yichen,Yasuike, Shuji,Kurita, Jyoji
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scheme or table
p. 436 - 438
(2009/12/25)
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- Highly active, well-defined (cyclopentadiene)(N-heterocyclic carbene)palladium chloride complexes for room-temperature Suzuki-Miyaura and Buchwald-Hartwig cross-coupling reactions of aryl chlorides and deboronation homocoupling of arylboronic acids
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A new class of well-defined N-heterocyclic carbene (NHC)-(cyclopentadiene) palladium chloride complexes such as CpPd(NHC)Cl wasw synthesized from the readily available starting NHC-palladium(II) chloride dimers. These air-stable, coordinatively saturated NHC-Pd complexes bearing the cyclopentadiene (Cp) unit exhibit high catalytic activity in the room temperature Suzuki-Miyaura and Buchwald-Hartwig cross-coupling reactions involving unactive aryl chlorides as the substrates. In addition, they are found to be extremely efficient catalysts in the deboronation homocoupling of arylboronic acids at room temperature.
- Jin, Zhong,Guo, Su-Xian,Gu, Xiao-Peng,Qiu, Ling-Ling,Song, Hai-Bing,Fang, Jian-Xin
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supporting information; experimental part
p. 1575 - 1585
(2011/02/28)
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- Nickel-catalyzed amination of aryl tosylates
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(Chemical Equation Presented) The cross-coupling of aryl tosylates with amines and anilines was accomplished by using a Ni-based catalyst system from the combination of Ni(II)-(σ-aryl) complexes/N-heterocyclic carbenes (NHCs). The feature, scope, and limitation of this reaction are disclosed.
- Gao, Cai-Yan,Yang, Lian-Ming
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p. 1624 - 1627
(2008/09/17)
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- Rapid and efficient Pd-catalyzed sonogashira coupling of aryl chlorides
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(Chemical Equation Presented) An efficient and effective microwave-assisted cross-coupling of terminal alkynes with various aryl chlorides including sterically hindered, electron-rich, electron-neutral, and electron-deficient aryl chloride is developed. It proceeds faster and generally gives good to excellent yields and also can be extended successfully to the Suzuki coupling and Buchwald-Hartwig amination, as well as the Heck coupling with inert aryl chlorides. The short reaction times and simple reaction conditions coupling with a broad substrate scope render this method particularly attractive for the efficient preparation of biologically and medicinally interesting molecules.
- Huang, He,Liu, Hong,Jiang, Hualiang,Chen, Kaixian
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p. 6037 - 6040
(2008/12/21)
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- Carbene adduct of cyclopalladated ferrocenylimine as an efficient catalyst for the amination of aryl chlorides
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A novel air- and moisture-stable carbene adduct of cyclopalladated ferrocenylimine has been synthesized and characterized. The structure of this compound was determined by X-ray crystal structure analysis. This adduct has been applied as an efficient catalyst for the amination of aryl chlorides.
- Li, Jingya,Cui, Mengjun,Yu, Ajuan,Wu, Yangjie
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p. 3732 - 3742
(2008/02/08)
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- Ni(II)-(σ-aryl) complex: A facile, efficient catalyst for nickel-catalyzed carbon-nitrogen coupling reactions
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(Chemical Equation Presented) trans-Haloarylbis(triphenylphosphine) nickel(II), a type of air-and moisture-stable Ni(II)-(σ-aryl) complex, was examined as catalyst precursor in the C-N coupling reaction. This type of Ni(II) pre-catalyst, associated with N-heterocyclic carbene ligands, is found to easily produce the catalytically active Ni(0) species in situ without the aid of external reductants and allows for the efficient amination of aryl chlorides with secondary cyclic amines and anilines under mild conditions.
- Chen, Chen,Yang, Lian-Ming
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p. 6324 - 6327
(2008/02/09)
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