- Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki-Miyaura reactions
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The energetically-favorable coordination of aldehydes and ketones-but not esters or amides-to Ni0 during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to inhibition of the reaction. Aryl halides w
- Cooper, Alasdair K.,Leonard, David K.,Bajo, Sonia,Burton, Paul M.,Nelson, David J.
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p. 1905 - 1911
(2020/03/03)
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- Nickel versus Palladium in Cross-Coupling Catalysis: On the Role of Substrate Coordination to Zerovalent Metal Complexes
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A detailed comparison of the effect of coordinating functional groups on the performance of Suzuki-Miyaura reactions catalysed by nickel and palladium is reported, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.
- Burton, Paul M.,Cooper, Alasdair K.,Nelson, David J.
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p. 565 - 573
(2020/02/13)
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- A Highly Efficient Monophosphine Ligand for Parts per Million Levels Pd-Catalyzed Suzuki–Miyaura Coupling of (Hetero)Aryl Chlorides
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A new indolylphosphine WK-phos has been synthesized for Pd-catalyzed Suzuki–Miyaura coupling of (hetero)aryl chlorides with (alkyl)arylboronic acids. Comprising this newly developed ligand with palladium(II) acetate, the resulting catalyst system was found to be highly effective in facilitating the reaction even when the catalyst loading reaches parts per million levels (e.g. 10 ppm). These examples represent one of the lowest catalyst loadings reported to date of employing monophosphine (e.g. Ar-PCy2) for Suzuki–Miyaura reactions. The ligand geometry has also been well-characterized by single-crystal X-ray crystallography.
- Choy, Pui Ying,Yuen, On Ying,Leung, Man Pan,Chow, Wing Kin,Kwong, Fuk Yee
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p. 2846 - 2853
(2020/04/09)
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- Selective Methylation of Arenes: A Radical C?H Functionalization/Cross-Coupling Sequence
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A selective, nonchelation-assisted methylation of arenes has been developed. The overall transformation, which combines a C?H functionalization reaction with a nickel-catalyzed cross-coupling, offers rapid access to methylated arenes with high para selectivity. The reaction is amenable to late-stage methylation of small-molecule pharmaceuticals.
- Serpier, Fabien,Pan, Fei,Ham, Won Seok,Jacq, Jér?me,Genicot, Christophe,Ritter, Tobias
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p. 10697 - 10701
(2018/07/31)
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- Highly bulky and stable geometry-constrained iminopyridines: Synthesis, structure and application in Pd-catalyzed Suzuki coupling of aryl chlorides
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A series of bulky geometry-constrained iminopyridylpalladium chlorides were developed. The steric environment adjacent to the nitrogen atom in the pyridine rings and diimine parts enhanced the thermal stability of the palladium species. Bulkier groups at the imino group stabilized the palladium species and the corresponding palladium chlorides showed high activities in the coupling reaction of aryl chlorides.
- Lai, Yi,Zong, Zhijian,Tang, Yujie,Mo, Weimin,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Jin, Liqun,Sun, Wen-Hua,Hu, Xinquan
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p. 213 - 221
(2017/02/15)
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- Phosphine ligand for indole skeleton as well as preparation method and application of phosphine ligand
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The invention provides a phosphine ligand for a 3-(disubstituted phosphino)-1-alkyl-2-substituted phenyl-indole skeleton as well as a preparation method and application of the phosphine ligand. The structure of the phosphine ligand for the 3-(disubstituted phosphino)-1-alkyl-2-substituted phenyl-indole skeleton is shown as the following formula I: (shown in the description), wherein Z is carbon or nitrogen, R is alkyl, substituted alkyl, olefin, aryl or fluorine, R1 is alkyl, substituted alkyl or aryl, R2 is alkyl, substituted alkyl or fluorine, and R3 is alkyl, substituted alkyl or aryl.
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Paragraph 0221-0226
(2017/12/30)
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- Ligand-free Pd catalyzed cross-coupling reactions in an aqueous hydrotropic medium
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A simple, efficient and ligand-free protocol for the Suzuki-Miyaura reaction and base-free Heck-Matsuda reactions under mild reaction conditions have been developed over palladium supported on activated carbon (Pd/C) in an aqueous hydrotropic solution. The catalyst Pd/C was fully characterized by TG-DTA, SEM, EDS, XRD, XPS, BET and ICP-AES analyses. This green methodology represents a cost-effective and operationally convenient method for the synthesis of a variety of biaryls, prochiral ketones, and acrylates under the conditions that are tolerant for a broad range of functional groups with good to excellent yields. The developed Pd/C-aqueous hydrotrope combined catalytic system is well suited for the 3R approach (reducible, robust, and recyclable) for different cross-coupling reactions without an appreciable loss of its activity.
- Jadhav, Sanjay N.,Kumbhar, Arjun S.,Rode, Chadrashekhar V.,Salunkhe, Rajashri S.
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supporting information
p. 1898 - 1911
(2016/04/19)
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- The Barbier-Grignard-Type Arylation of Ketones and Unexpected Cross-Coupling of Phenolic Ketones using Unactivated Aryl Bromides
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A novel, highly versatile and efficient method has been developed for the Barbier-Grignard-type arylation of ketones and an unexpected cross-coupling of phenolic ketones was observed using unactivated bromides and magnesium in tetrahydrofuran/toluene at 96°C promoted by multicatalysts of cupric bromide (15 mol%), bismuth chloride (5 mol%) and silver bromide (10 mol%). The substituent and electronic effects on the reaction have been discussed. High yields of arylation and cross-coupling have been attained under mild conditions. A novel reasonable mechanism involving a quinone intermediate is proposed. The high chemical selectivity in the cross-coupling to the hydroxy group of phenolic ketones should help ketones find new applications.
- Wen, Yunming,Chen, Guifang,Huang, Shiqiang,Tang, Yu,Yang, Jun,Zhang, Yuanming
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p. 947 - 957
(2016/04/05)
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- Pincer-Nickel-Catalyzed Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides
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The nickel N,N,N-pincer complex 2 was demonstrated to effectively catalyze the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups. A nickel N,N,N-pincer complex effectively catalyzes the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups.
- Tao, Jian-Long,Wang, Zhong-Xia
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p. 6534 - 6540
(2015/10/19)
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- Mono- and dinuclear pincer nickel catalyzed activation and transformation of C-Cl, C-N, and C-O bonds
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Condensation of 2-NH2C6H4P(Et)Ph (2) with pyrrole-2-carboxaldehyde generated 2-(C4H4N-2′-CH - N)C6H4P(Et)Ph (3). Treatment of 3 with NaH and followed by (DME)NiX2 (X = Cl, Br) afforded mononuclear pincer nickel complexes [Ni{2-(C4H3N-2′-CH - N)C6H4P(Et)Ph}X] (4a, X = Cl; 4b, X = Br). Reaction of [2-NH2C6H4P(Ph)]2(CH2)n (5a, n = 3; 5b, n = 4) with pyrrole-2-carboxaldehyde or 5-tert-butyl-1H-pyrrole-2-carbaldehyde formed [2-(C4H4N-2′-CH - N)C6H4P(Ph)]2(CH2)n (6a, n = 3; 6b, n = 4) and [2-(5′-tBuC4H3N-2′-CH - N)C6H4P(Ph)]2(CH2)4 (6c). Respective treatment of 6a-c with NaH followed by (DME)NiX2 (X = Cl, Br) gave the dinuclear nickel complexes [Ni{2-(5′-RC4H2N-2′-CH - N)C6H4P(Ph)}X]2(CH2)n (7a, R = H, X = Cl, n = 3; 7b, R = H, X = Cl, n = 4; 7c, R = H, X = Br, n = 4; 7d, R = tBu, X = Cl, n = 4). Catalysis of the complexes for the activation and transformation of C-Cl, C-N, and C-O bonds was evaluated. Complex 7c exhibited excellent catalytic activity in the cross-coupling of aryl chlorides or aryltrimethylammonium iodides with arylzinc reagents as well as of aryl sulfamates with aryl Grignard reagents. The dinuclear nickel complexes 7b-d showed higher catalytic activity than the mononuclear complexes in each type of reaction.
- Yang, Xia,Wang, Zhong-Xia
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p. 5863 - 5873
(2015/01/09)
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- P,N,N-Pincer nickel-catalyzed cross-coupling of aryl fluorides and chlorides
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P,N,N-Pincer nickel complexes [Ni(Cl){N(2-R2PC6H 4)(2′-Me2NC6H4)}] (R = Ph, 3a; R = Pri, 3b; R = Cy, 3c) were synthesized and their catalysis toward the Kumada or Negishi cross-coupling reaction of aryl fluorides and chlorides was evaluated. Complex 3a effectively catalyzes the cross-coupling of (hetero)aryl fluorides with aryl Grignard reagents at room temperature. Complex 3a also catalyzes the cross-coupling of (hetero)aryl chlorides and arylzinc reagents at 80 °C with low catalyst loadings and good functional group compatibility. the Partner Organisations 2014.
- Wu, Dan,Wang, Zhong-Xia
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p. 6414 - 6424
(2014/08/18)
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- Nickel-catalyzed cross-coupling of aryl fluorides and organozinc reagents
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Ni(PCy3)2Cl2 was demonstrated to effectively catalyze cross-coupling of aryl fluorides and organozinc reagents. Both electron-poor and -rich aryl fluorides can react effectively with nucleophiles including aryl-, methyl-, and benzylzinc chlorides. A wide range of substituents and functional groups are tolerated. In the presence of a directing group, PhC(O), the reaction is selective for cleavage of the C-F bond ortho to the carbonyl substituent in a difluoroarene.
- Zhu, Feng,Wang, Zhong-Xia
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p. 4285 - 4292
(2014/06/09)
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- An efficient class of P,N-type "phMezole-phos" ligands: Applications in palladium-catalyzed Suzuki coupling of aryl chlorides
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This study describes an efficient class of hemilabile benzimidazolyl- phosphane ligands that can be easily accessed from commercially available and inexpensive starting materials. The application of this ligand array in the palladium-catalyzed Suzuki-Miyaura coupling reaction of aryl chlorides with arylboronic acids is described. The palladium catalyst generated from this hemilabile phosphane is highly effective in the Suzuki-Miyaura coupling of unactivated aryl chlorides, and catalyst loadings as low as 1 ppm can be achieved. An efficient class of hemilabile benzimidazolyl-phosphane ligands were synthesized. The palladium catalyst generated from this hemilabile phosphane is highly effective in the Suzuki-Miyaura coupling of unactivated aryl chlorides, and catalyst loadings as low as 1 ppm can be achieved.
- Wong, Shun Man,So, Chau Ming,Chung, Kin Ho,Lau, Chak Po,Kwong, Fuk Yee
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supporting information; experimental part
p. 4172 - 4177
(2012/09/21)
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- Cross-coupling of aryltrimethylammonium iodides with arylzinc reagents catalyzed by amido pincer nickel complexes
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The cross-coupling reaction of aryltrimethylammonium iodides with aryl- or heteroarylzinc chlorides catalyzed by amido pincer nickel complexes was performed. The reaction requires low catalyst loading and displays broad substrate scope.
- Zhang, Xue-Qi,Wang, Zhong-Xia
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experimental part
p. 3658 - 3663
(2012/05/20)
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- Nickel complexes supported by quinoline-based ligands: Synthesis, characterization and catalysis in the cross-coupling of arylzinc reagents and aryl chlorides or aryltrimethylammonium salts
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Lithium and nickel complexes bearing quinoline-based ligands have been synthesized and characterized. Reaction of 8-azidoquinoline with Ph 2PNHR (R = p-MeC6H4, But) affords N-(8-quinolyl)iminophosphoranes RNHP(Ph2)N(8-C9H 6N) (1a, R = p-MeC6H4; 1b, R = But. C9H6N = quinolyl)). Reaction of 1a with (DME)NiCl 2 generates a nickel complex [NiCl2{N(8-C 9H6N)P(Ph2)NH(p-MeC6H4)}] (2a). Treatment of 1b with (DME)NiCl2 and following with NaH produces [NiCl{(1,2-C6H4)P(Ph)(NHBut)N(8-C 9H6N)}] (4). Complex 4 was also obtained by reaction of (DME)NiCl2 with [Li{(1,2-C6H4)P(Ph)(NHBu t)N(8-C9H6N)}] (5) prepared through lithiation of 1b. Reaction of 2-PyCH2P(Ph2)N(8-C9H 6N) (6, Py = pyridyl) and PhNC(Ph)CH2P(Ph 2)N(8-C9H6N) (8), respectively, with (DME)NiCl2 yields two five-coordinate N,N,N-chelate nickel complexes, [NiCl2{2-PyCH2P(Ph2)N(8-C9H 6N)}] (7) and [NiCl2{PhNC(Ph)CH2P(Ph 2)N(8-C9H6N)}] (9). Similar reaction between Ph2PCH2P(Ph2)N(8-C9H6N) (10) and (DME)NiCl2 results in five-coordinate N,N,P-chelate nickel complex [NiCl2{Ph2PCH2P(Ph2)N(8- C9H6N)}] (11). Treatment of [(8-C9H 6N)NP(Ph2)]2CH2 (12) [prepared from (Ph2P)2CH2 and 2 equiv. of 8-azidoquinoline] with LiBun and (DME)NiCl2 successively affords [NiCl{(8-C9H6N)NP(Ph2)}2CH] (13). The new compounds were characterized by 1H, 13C and 31P NMR spectroscopy (for the diamagnetic compounds), IR spectroscopy (for the nickel complexes) and elemental analysis. Complexes 2a, 4, 7, 9, 11 and 13 were also characterized by single-crystal X-ray diffraction techniques. The nickel complexes were evaluated for the catalysis in the cross-coupling reactions of arylzinc reagents with aryl chlorides and aryltrimethylammonium salts. Complex 7 exhibits the highest activity among the complexes in catalyzing the reactions of arylzinc reagents with either aryl chlorides or aryltrimethylammonium bromides.
- Zhang, Qiang,Zhang, Xue-Qi,Wang, Zhong-Xia
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p. 10453 - 10464,12
(2020/08/31)
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- Nickel-catalyzed Suzuki-Miyaura reaction of aryl fluorides
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Two protocols for the nickel-catalyzed cross-coupling of aryl fluorides with aryl boronic esters have been developed. The first employs metal fluoride cocatalysts, such as ZrF4 and TiF4, which enable Suzuki-Miyaura reactions of aryl fluorides bearing electron-withdrawing (ketones, esters, and CF3), aryl and alkenyl groups as well as those comprising fused aromatic rings, such as fluoronaphthalenes and fluoroquinolines. The second protocol employs aryl fluorides bearing ortho-directing groups, which facilitate the difficult C-F bond activation process via cyclometalation. N-heterocycles, such as pyridines, quinolines, pyrazoles, and oxazolines, can successfully promote cross-coupling with an array of organoboronic esters. A study into the substituent effects with respect to both coupling components has provided fundamental insights into the mechanism of the nickel-catalyzed cross-coupling of aryl fluorides.
- Tobisu, Mamoru,Xu, Tian,Shimasaki, Toshiaki,Chatani, Naoto
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supporting information; experimental part
p. 19505 - 19511
(2012/01/31)
-
- Kumada coupling of aryl, heteroaryl, and vinyl chlorides catalyzed by amido pincer nickel complexes
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A series of amido pincer complexes of nickel were examined for their catalysis in the Kumada cross-coupling reaction. The P,N,O-pincer nickel complexes tested are active catalysts for the cross-coupling of aryl, heteroaryl, and vinyl chlorides with aryl Grignard reagents. The reactions can proceed at room temperature and tolerate functional groups in aryl chlorides with the aid of LiCl and ZnCl2 additives (Figure presented).
- Liu, Ning,Wang, Zhong-Xia
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experimental part
p. 10031 - 10038
(2012/02/05)
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- Nickel-catalyzed cross-coupling of aryltrimethylammonium iodides with organozinc reagents
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Broad scope and good tolerance: An efficient cross-coupling of aryltrimethylammonium iodide salts with aryl-, methyl-, and benzylzinc chlorides catalyzed by [Ni(PCy3)2Cl2] has been achieved (see scheme). The reaction involves cleavage of the C-N bond and displays broad substrate scope and good functional group tolerance. NMP=N-methylpyrrolidine. Copyright
- Xie, Lan-Gui,Wang, Zhong-Xia
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supporting information; experimental part
p. 4901 - 4904
(2011/06/22)
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- Room-temperature nickel-catalysed cross-couplings of aryl chlorides with arylzincs
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P,N,O-chelate nickel complexes efficiently catalyse the cross-coupling reaction of aryl chlorides with arylzinc reagents in a 11 THF-NMP mixture. The reactions proceed at room temperature with low catalyst loading.
- Liu, Ning,Wang, Li,Wang, Zhong-Xia
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supporting information; scheme or table
p. 1598 - 1600
(2011/03/20)
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- Nickel-catalyzed cross-coupling of non-activated or functionalized aryl halides with aryl grignard reagents
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Figure Presented New nickel complexes can efficiently catalyze cross-coupling of unactivated and deactivated aryl chlorides and fluorides with aryl Grignard reagents. The reaction can tolerate functional groups in aryl chlorides with or without the aid of additives, depending on the substrates (see scheme).
- Xie, Lan-Gui,Wang, Zhong-Xia
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supporting information; experimental part
p. 10332 - 10336
(2010/10/21)
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- A general palladium catalyst system for suzuki-miyaura coupling of potassium aryltrifluoroborates and aryl mesylates
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(Figure presented) The first general examples of palladium-catalyzed Suzuki-type cross-coupling of aryl and heteroaryl mesylates with potassium aryl and heteroaryltrifluoroborates are presented. In addition to biaryl couplings, the cross-coupling reactions of aryl mesylates with alkyl and vinyltrifluoroborate salts have also been successfully accomplished.
- Chow, Wing Kin,So, Chau Ming,Lau, Chak Po,Kwong, Fuk Yee
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supporting information; scheme or table
p. 5109 - 5112
(2010/09/05)
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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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- A new palladium catalyzed protocol for atom-efficient cross-coupling reactions of?triarylbismuths with aryl halides and triflates
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A new palladium catalyzed protocol for an atom-efficient cross-coupling reaction of triarylbismuths with aryl halides and triflates has been described. The palladium catalytic system with Cs2CO3 base was found to be very efficient in DMA solvent to furnish excellent yields of cross-coupled functionalized biaryls in short reaction times.
- Rao, Maddali L.N.,Jadhav, Deepak N.,Banerjee, Debasis
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p. 5762 - 5772
(2008/09/21)
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- Solventless Suzuki coupling reactions on palladium-doped potassium fluoride alumina
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A solventless Suzuki coupling reaction has been developed which utilizes a commercially available potassium fluoride alumina mixture and palladium powder. The new reaction is convenient, environmentally friendly, and generates good yields of the coupled products. Aryl iodides react faster than the bromides or chlorides; aryl groups are also more reactive than alkenyl groups, which react faster than alkyl groups. The use of microwave irradiation accelerates the reaction, decreasing reaction times from hours to minutes. The palladium powder catalyst can be recycled using a simple filtration and washing sequence without loss of catalytic activity.
- Kabalka, George W.,Wang, Lei,Pagni, Richard M.,Hair, C. Maxwell,Namboodiri, Vasudevan
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p. 217 - 222
(2007/10/03)
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- Substituted aminoalkyl biphenyl compounds and method of treating fungal infections
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Antimycotically-active compounds of the formula STR1 wherein R1 and R2 each independently are hydrogen, C1-7 -alkyl or C2-7 -alkenyl or together are a straight chain C2-4 -alkylene; R3 and R4 each independently are hydrogen or C1-7 -alkyl; R5 and R6 each independently are hydrogen, halogen, trifluoromethyl, nitro, cyano, C1-7 -alkoxy or C1-7 -alkyl; and Q is an unsubstituted or substituted phenyl or naphthyl group, wherein the substituents are at least one of halogen, trifluoromethyl, cyano, nitro, C1-7 -alkyl, C1-7 -alkoxy; C2-10 -alkenyl; or a substituted or unsubstituted C1-10 -alkyl group wherein said substituents are at least one hydroxy group; and pharmaceutically acceptable acid addition salts thereof.
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