- 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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- Synthesis of N-heterocyclic carbene-Pd(II)-5-phenyloxazole complexes and initial studies of their catalytic activity toward the Buchwald-Hartwig amination of aryl chlorides
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Three new N-heterocyclic carbene (NHC)-Pd(II) complexes using 5-phenyloxazole as the ancillary ligand have been obtained in moderate to good yields by a one-pot reaction of the corresponding imidazolium salts, palladium chloride and 5-phenyloxazole under mild conditions. Initial studies showed that one of the complexes is an efficient catalyst for the Buchwald-Hartwig amination of aryl chlorides with various secondary and primary amines under the varied catalyst loading of 0.01-0.05 mol%, thus it will enrich the chemistry of NHCs and give an alternative catalyst for the coupling of challenging while cost-low aryl chlorides.
- Zhang, Zhi-Mao,Xu, Yu-Ting,Shao, Li-Xiong
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- N-Heterocyclic carbene-palladacyclic complexes: synthesis, characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides
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N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01 mol%).
- Liu, Feng,Hu, Yuan-Yuan,Li, Di,Zhou, Quan,Lu, Jian-Mei
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p. 5683 - 5690
(2018/08/24)
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- NOVEL COMPOUND, COLORING COMPOSITION FOR DYEING OR TEXTILE PRINTING, INK JET INK, METHOD OF PRINTING ON FABRIC, AND DYED OR PRINTED FABRIC
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Provided are a compound represented by any one of Formulae (1) to (3) (for example, the following compound), a coloring composition for dyeing or textile printing including the compound, an ink jet ink including the coloring composition for dyeing or text
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Paragraph 0424; 0425
(2017/05/10)
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- N-heterocyclic carbene-palladium complex, and preparation method and application thereof
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The invention discloses an N-heterocyclic carbene-palladium complex, and a preparation method and application thereof. The N-heterocyclic carbene-palladium complex disclosed by the invention is shown in Formula (I), wherein L1 is a quinoline ligand or isoquinoline ligand, and N in the L1 is connected with Pd; L2 is an N-heterocyclic carbene ligand, and carbene carbon in the L2 is connected with the Pd; and X1 and X2 are respectively independently an anionic ligand. The N-heterocyclic carbene-palladium complex disclosed by the invention can efficiently catalyze carbon-carbon or carbon-heteroatom coupling reaction using aryl halide as a substrate. The formula is shown in the specification.
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Paragraph 0140; 0141; 0142
(2017/07/22)
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- Organonickel complexes encumbering bis-imidazolylidene carbene ligands: Synthesis, X-ray structure and catalytic insights on Buchwald-Hartwig amination reactions
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New four coordinated homoleptic bis(diimidazolylidene)nickel(II) complexes (C1 & C2) were synthesized and characterized by elemental analysis, NMR (1H and13C) as well as ESI-Mass spectrometry. The molecular structure of the complex C1 was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted square planar geometry with chelating bis(diimidazolylidene) NHC ligands and two non coordinating bromide counter ions in tetradentate C4fashion. A survey of their catalytic activity in Buchwald?Hartwig amination has been performed. The newly synthesized complexes also catalyzed the amination of aryl chlorides in the presence of KOtBu. Various aryl chlorides and amines can react smoothly to give the corresponding aminated products in moderate to high yields. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine and quinoline derivatives. Both secondary and primary amines are well tolerated under the optimal reaction conditions.
- Nirmala, Muthukumaran,Saranya, Gandhi,Viswanathamurthi, Periasamy,Bertani, Roberta,Sgarbossa, Paolo,Malecki, Jan Grzegorz
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supporting information
p. 1 - 10
(2017/01/09)
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- Synthesis of N-heterocyclic carbene-Pd(II) complexes and their catalytic activity in the Buchwald-Hartwig amination of aryl chlorides
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Novel N-heterocyclic carbene-palladium(II) complexes using 2-picolinic acid as the ancillary ligand have been successfully developed under mild conditions. Their catalytic activity in organic synthesis has been initially tested in the Buchwald-Hartwig amination of secondary and primary amines with aryl chlorides. Various substituents on both substrates can be tolerated, giving the desired coupling products in good to almost quantitative yields. The minimum catalyst loading can be 0.01 mol%, implying their potential application toward industrial processes.
- Zhang, Zhi-Mao,Gao, Yu-Jue,Lu, Jian-Mei
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p. 7308 - 7314
(2017/12/01)
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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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- COLORING COMPOSITION, INKJET INK, FABRIC PRINTING METHOD, AND DYED OR PRINTED FABRIC
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PROBLEM TO BE SOLVED: To provide a coloring composition having excellent light resistance and excellent storage stability, inkjet ink comprising the coloring composition, a fabric printing method, and a dyed or printed fabric. SOLUTION: The present invent
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Paragraph 0271; 0272; 0273
(2017/06/02)
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- Synthesis and characterization of N-heterocyclic carbene-palladium(II) chlorides-1-methylindazole and -1-methylpyrazole complexes and their catalytic activity toward C-N coupling of aryl chlorides
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A series of N-heterocyclic carbene-palladium(ii) chlorides-1-methylindazole and -1-methylpyrazole complexes was successfully synthesized and fully characterized by X-ray single crystal diffraction. In addition, initial investigations of their catalytic activity showed that they were efficient catalysts in the C-N coupling of primary and secondary amines with aryl chlorides at low catalyst loadings.
- Zhao, Xiao-Yun,Zhou, Quan,Lu, Jian-Mei
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p. 24484 - 24490
(2016/03/15)
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- Synthesis of N-heterocyclic carbene-PdCl2-(iso)quinoline complexes and their application in arylamination at low catalyst loadings
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A new type of N-heterocyclic carbene-PdCl2-(iso)quinoline complexes 3 were successfully achieved in acceptable to good yields from easily available starting materials under mild conditions, and their structures were unambiguously confirmed using X-ray single crystal diffraction. Furthermore, their catalytic activity toward Buchwald-Hartwig arylamination of aryl chlorides with primary and secondary amines was fully tested. Under the optimal reaction conditions, the expected arylated amines can be obtained in high to excellent yields at low catalyst loadings (0.005-0.05 mol%). It may be worth noting here that comparison of these complexes with other well-defined and easily available NHC-Pd(ii) complexes bearing different N-containing ancillary ligands was also carried out, showing their superior catalytic activity over all others.
- Liu, Feng,Zhu, Yi-Ran,Song, Lu-Gan,Lu, Jian-Mei
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p. 2563 - 2571
(2016/03/01)
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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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- A tuned bicyclic proazaphosphatrane for catalytically enhanced n-arylation reactions with aryl chlorides
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The N-arylation of various amines with aryl chlorides proceeded in good-to-excellent yields in the presence of P[N{(p-NMe2)C6H4CH2}CH2CH2]3N (1e, a new electron-rich proazaphosphatrane ligand) and small amounts of Pd2(dba)3 (dba = dibenzylideneacetone). This catalytic system was also very effective for the synthesis of carbazoles. An efficient palladium-catalyzed N-arylation reaction of amines under mild conditions with a tuned bicyclic proazaphosphatrane has been developed.
- Kim, So Han,Kim, Min,Verkade, John G.,Kim, Youngjo
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p. 1954 - 1960
(2015/03/18)
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- [Pd(IPr*OMe)(acac)Cl]: Tuning the N-heterocyclic carbene in catalytic C-N bond formation
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A new N-heterocyclic ligand IPr*OMe [N,N′-bis(2,6- bis(diphenylmethyl)-4-methoxyphenyl)imidazol-2-ylidene] has been synthesized and compared with its earlier methyl-substituted congener IPr* [N,N′-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene]. IPr*OMe was successfully bound to palladium, and the catalytic activity of the resulting complex [Pd(IPr*OMe)(acac)Cl] was investigated in Buchwald-Hartwig arylamination. Catalytic activity was compared to that of [Pd(IPr*)(acac)Cl].
- Meiries, Sebastien,Speck, Klaus,Cordes, David B.,Slawin, Alexandra M. Z.,Nolan, Steven P.
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p. 330 - 339
(2013/02/25)
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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)
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- [Pd(IPr*)(acac)CI]: An easily synthesized, bulky precatalyst for C-N bond formation
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A very straightforward synthesis of [Pd(IPr*)(acac)Cl] has been developed from commercially available Pd(acac)2 and the easily prepared IPr*·HCl (acac = acetylacetonate; IPr* = N,N′-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene). The reactivity of the resulting complex [Pd(IPr*)(acac)Cl] (1) as a highly active PdII precatalyst for the Buchwald-Hartwig arylamination coupling has been explored. A wide range of substrates with varying electronic and steric demands of both coupling partners has been screened successfully. The chemoselectivity of the reaction was also explored by using aryl heterodihalides.
- Meiries, Sebastien,Chartoire, Anthony,Slawin, Alexandra M. Z.,Nolan, Steven P.
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experimental part
p. 3402 - 3409
(2012/06/04)
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- Well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides
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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
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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)
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- An efficient palladium-NHC (NHC=N-heterocyclic carbene) and aryl amination pre-catalyst: [Pd(IPr*)(cinnamyl)Cl]
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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)
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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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- A novel and efficient PEPPSI precatalyst
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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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- 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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- Highly active well-defined palladium precatalysts for the efficient amination of aryl chlorides
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The efficient preparation of [Pd(Amphos)(cinnamyl)Cl)] and [Pd(Amphos)(TFA)(κ2-N,C-C6H4-CH 2NMe2)] (Amphos = 4-(di-tert-butylphosphino)-N,N- dimethylaniline and TFA = trifluoroacetate), two new well-defined palladium precatalysts, is reported. These complexes prove highly active in the Buchwald-Hartwig amination reaction, allowing the coupling of a wide range of (hetero)aryl chlorides, including unactivated, neutral, and sterically hindered substrates, with a wide range of amines, including primary and secondary amines. Finally, the catalytic systems have proven efficient at low catalyst loadings ranging from 0.1 to 0.3 mol %.
- Chartoire, Anthony,Lesieur, Mathieu,Slawin, Alexandra M. Z.,Nolan, Steven P.,Cazin, Catherine S. J.
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experimental part
p. 4432 - 4436
(2011/10/10)
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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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- (t-Bu)2PN=P(i-BuNCH2CH2)3N: New efficient ligand for palladium-catalyzed C-N couplings of aryl and heteroaryl bromides and chlorides and for vinyl bromides at room temperature
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(Chemical Equation Presented) By employing Pd(OAc)2, Cs 2CO3, or NaOH, and the new ligand (t-Bu) 2PN=P(i-BuNCH2CH2)3N (3a), an electronically diverse array of aryl bromides and chlorides possessing base-sensitive substituents (nitro, ester, and keto) provide coupling products with bulky aryl amines in good to excellent yields. Aryl halides possessing other functional groups including cyano, amino, trifluoromethyl, and phenol, coupled with equal ease, producing highly functionalized amines in good to excellent yields. Moreover, an aryl chloro group can be preserved in the presence of a bromo substituent under our reaction conditions. BOC-protected amines also participated efficiently. Heterocyclic bromides and chlorides underwent clean couplings with amines in excellent yields. An important strength of our protocol is the use of lower palladium loadings than those reported earlier, without compromising yields. The air-stable palladium complex (η3-cinnamyl)PdCl·(3a) (5) was also employed successfully in C-N coupling reactions while the crotyl analogue was less efficacious. The 3a/Pd(OAc)2 catalyst system promotes, for the first time, efficient coupling of vinyl bromides with a variety of amines to produce imines and enamines at room temperature.
- Reddy, Ch. Venkat,Kingston, Jesudoss V.,Verkade, John G.
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p. 3047 - 3062
(2008/09/19)
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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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- A diaminochlorophosphine for palladium-catalyzed arylations of amines and ketones
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(Chemical Equation Presented) Sterically hindered substituents on a secondary chlorophosphine 1 prevent formation of a diaminooxophosphine, and thereby allow for highly efficient arylation reactions of amines and α-C-H acidic ketones with (hetero)aryl chlorides.
- Ackermann, Lutz,Spatz, Julia H.,Gschrei, Christian J.,Born, Robert,Althammer, Andreas
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p. 7627 - 7630
(2007/10/03)
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- Modified (NHC)Pd(allyl)Cl (NHC = N-heterocyclic carbene) complexes for room-temperature Suzuki-Miyaura and Buchwald-Hartwig reactions
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A series of (NHC)Pd(R-allyl)Cl complexes [NHC: IPr = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene, SIPr = N,N′-bis(2,6- diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene; R = H, Me, gem-Me2, Ph] have been synthesized and fully characterized. When compared to (NHC)Pd(allyl)Cl, substitution at the terminal position of the allyl scaffold favors a more facile activation step. This translates into higher catalytic activity in the Suzuki-Miyaura and Buchwald-Hartwig reactions, allowing for the coupling of unactivated aryl chlorides at room temperature in minutes. In the Suzuki-Miyaura reaction, aryl triflates, bromides, and chlorides react with boronic acids using very low catalyst loading. In the N-aryl amination reaction, a wide range of substrates has been coupled efficiently; primary-, secondary-, alkyl-, or aryl-amines react in high yields with unactivated, neutral, and activated aryl chlorides and bromides. In both reactions, extremely hindered substrates such as tri-ortho-substituted biaryls and tetra-ortho-substituted diarylamines can be produced without loss of activity. Finally, the present catalytic system has proven to be efficient with as low as 10 parts-per-million (ppm) of precatalyst in the Buchwald-Hartwig reaction and 50 ppm in the Suzuki-Miyaura reaction.
- Marion, Nicolas,Navarro, Oscar,Mei, Jianguo,Stevens, Edwin D.,Scott, Natalie M.,Nolan, Steven P.
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p. 4101 - 4111
(2007/10/03)
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- (IPr)Pd(acac)Cl: An easily synthesized, efficient, and versatile precatalyst for C-N and C-C bond formation
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A very straightforward synthesis of (IPr)Pd(acac)Cl from two commercially available starting materials, Pd(acac)2 and IPr·HCl [acac = acetylacetonate; IPr = N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], has been developed. The resulting complex, (IPr)Pd(acac)Cl (1), has proven to be a highly active PdII precatalyst in the Buchwald-Hartwig and the α-ketone arylation reactions. A wide range of substrates has been screened, including unactivated, sterically hindered, and heterocyclic aryl chlorides.
- Marion, Nicolas,Ecarnot, Elise C.,Navarro, Oscar,Amoroso, Dino,Bell, Andrew,Nolan, Steven P.
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p. 3816 - 3821
(2007/10/03)
-
- NUCLEOPHILIC HETEROCYCLIC CARBENE DERIVATIVES OF PD(ACAC)2 FOR CROSS-COUPLING REACTIONS
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Embodiments in accordance with the present invention provide for a palladium complex characterized by the general Formula (I): where A is a bidentate monoanionic ligand, NHC is a nucleophilic heterocyclic carbene, and Z is an anionic ligand. Such palladium complexes are useful in initiating cross-coupling reactions.
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Page/Page column 17, 32, 36
(2010/11/25)
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- Buchwald-Hartwig aminations of aryl chlorides: A practical protocol based on commercially available Pd(0)-NHC catalysts
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Commercially available, air- and water-stable naphthoquinone imidazolin-2-ylidene-palladium(0) complexes were found to be highly active one-component catalysts for the amination of aryl halides. With these very robust catalysts, the expensive bases Cs2CO3 or NaOt-Bu traditionally used can be replaced by KOH. A convenient reaction protocol has been developed for the coupling of a wide range of aryl chlorides with primary or secondary amines.
- Goo?en,Paetzold,Briel,Rivas-Nass,Karch,Kayser
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p. 275 - 278
(2007/10/03)
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- Scope and limitations of Pd2(dba)3/P(i-BuNCH 2CH2)3N-catalyzed Buchwald-Hartwig amination reactions of aryl chlorides
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Proazaphosphatrane ligands in combination with Pd2(dba) 3 generate highly active catalysts for Buchwald-Hartwig amination of aryl chlorides. In particular, commercially available P(i-BuNCH 2-CH2)3N is a highly general and efficient ligand, allowing the coupling of an electronically diverse set of aryl chlorides, including chloropyridines, with a wide variety of amines using 1 mol % of Pd at 100 °C. Either a 1:1 or 2:1 ratio of ligand to Pd was found to be effective. This catalyst system performs exceptionally well for sterically hindered substrates, even with only 0.25 mol % of Pd. It is shown that NaOH can also be used as the base (instead of NaO-t-Bu) allowing functionalized substrates to participate in these reactions.
- Urgaonkar, Sameer,Verkade, John G.
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p. 9135 - 9142
(2007/10/03)
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- A new efficient palladium catalyst for the amination of aryl chlorides
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A highly active catalyst for the Buchwald-Hartwig amination has been developed. The new catalyst, a combination of a dimethylaminomethyl ferrocene palladacycle and bis(2-nor-bornyl)phosphine shows high activity and broad scope for the coupling of non- or deactivated aryl chlorides with primary and secondary amines as well as (hindered) anilines.
- Nettekoven, Ulrike,Naud, Frédéric,Schnyder, Anita,Blaser, Hans-Ulrich
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p. 2549 - 2552
(2007/10/03)
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- High turnover number and rapid, room-temperature amination of chloroarenes using saturated carbene ligands
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Pd(dba)2, 0.02-2 mol% Ligand 1, 0.08-2 mol% ArCl + NHRR′ → Ar-NRR′ NaO-t Bu, DME Ar = unactivated aryl, rt-100°C (71%-quant.) heteroaryl NHRR′ = 1° and 2° aryl; 2° acyclic and cyclic alkyl; imino A catalytic system for the mild amination of aryl chlorides is described. This system consists of a Pd(0) precursor and a dihydroimidazoline carbene ligand, which is generated in situ from its protonated tetrafluoroborate salt (2). Using this catalyst, aryl and heteroaryl chlorides react with secondary amines and anilines within hours at room temperature. Turnover numbers as high as 5000 are obtained at elevated temperatures for reaction of morpholine with an unactivated aryl chloride.
- Stauffer, Shaun R.,Lee, Sunwoo,Stambuli, James P.,Hauck, Sheila I.,Hartwig, John F.
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p. 1423 - 1426
(2007/10/03)
-