- Effect of Precatalyst Oxidation State in C-N Cross-Couplings with 2-Phosphinoimidazole-Derived Bimetallic Pd(I) and Pd(II) Complexes
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We report the catalytic activity of two phosphinoimidazole-derived bimetallic palladium complexes in Pd-catalyzed amination reactions. Our studies demonstrate that the starting oxidation state (Pd(I) or Pd(II)) of the dimeric complex has a significant effect on the efficiency of the catalytic reaction. The corresponding Pd(I) complex shows higher reactivity in Buchwald-Hartwig aminations, while the Pd(II) complex is much more reactive in carbonylative amination reactions. These new dimeric palladium complexes provide good to excellent reactivity and yields in the amination reactions tested.
- Martinez, Erin E.,Moreno, Mariur Rodriguez,Barksdale, Caleb A.,Michaelis, David J.
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supporting information
p. 2763 - 2767
(2021/08/27)
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- Amination of Aryl Halides Mediated by Electrogenerated Nickel from Sacrificial Anode
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Electrochemical C(sp2)?N couplings mediated by nickel salts generated from the sacrificial anode has been described for the first time. In this approach, the sacrificial nickel anode is employed as the sole source of nickel and the process, operationally simple to set up, enables the preparation of functionalized arylamine derivatives with moderate to good yields, under mild reaction conditions and without additional ligand. A cooperative process between the two electrodes is involved in the proposed mechanism.
- Daili, Farah,Sengmany, Stéphane,Léonel, Eric
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p. 2462 - 2469
(2021/06/28)
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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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- Electrochemical Cross-Dehydrogenative Aromatization Protocol for the Synthesis of Aromatic Amines
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The introduction of amines onto aromatics without metal catalysts and chemical oxidants is synthetically challenging. Herein, we report the first example of an electrochemical cross-dehydrogenative aromatization (ECDA) reaction of saturated cyclohexanones and amines to construct anilines without additional metal catalysts and chemical oxidants. This reaction exhibits a broad scope of cyclohexanones including heterocyclic ketones, affording a variety of aromatic amines with various functionalities, and shows great potential in the synthesis of biologically active compounds.
- Chen, Hua,Chen, Shan-Yong,Feng, Mei-Lin,Fu, Hai-Yan,Li, Rui-Xiang,Tao, Shao-Kun,Xu, Jia-Qi,Yu, Xiao-Qi,Yuan, Mao-Lin,Zheng, Xue-Li
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supporting information
(2022/02/05)
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- Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
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It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
- Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
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p. 3421 - 3426
(2020/06/25)
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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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- Ru(II)-Catalyzed Amination of Aryl Fluorides via η6-Coordination
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We developed a Ru/hemilabile-ligand-catalyzed nucleophilic aromatic substitution (SNAr) of aryl fluorides as the limiting reagents. Significant ligand enhancement was demonstrated by the engagement of both electron-rich and neutral arenes in the SNAr amination without using excess arenes. Preliminary mechanistic studies revealed that the nucleophilic substitution proceeds on a η6-complex of the Ru catalyst and the substrate, and the hemilabile ligand facilitates dissociation of products from the metal center.
- Kang, Qi-Kai,Li, Yuntong,Lin, Yunzhi,Shi, Hang
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supporting information
p. 3706 - 3711
(2020/03/11)
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- Photo-induced dealdehyding method
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The invention provides a photo-induced dealdehyding method, and belongs to the technical field of organic synthesis. The photo-induced dealdehyding method comprises the following steps that a mixtureof a compound shown in the formula I and a solvent are reacted under an inert gas atmosphere and visible light irradiation, a dealdehyding product is obtained, and no photocatalyst is used in the whole process; wherein the structural formula of the formula I shown in the specification, R is a functional group and is selected from hydrogen, methyl, methoxyl, cyano, chlorine, bromine or fluorine. According to the photo-induced dealdehyding method, in the inert gas atmosphere, the compound shown in the formula (I) can be excited to generate carbon-oxygen bond homogeneous cracking through visiblelight irradiation, then free radical migration and double bond displacement are conducted, finally carbon monoxide is removed, aldehyde group removal is completed, no photocatalyst is needed in the whole process, operation is easy and convenient, and conditions are mild.
- -
-
Paragraph 0048-0053; 0102-0107
(2020/06/16)
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- Redox-neutral: Ortho -C-H amination of pinacol arylborates via palladium(ii)/norbornene catalysis for aniline synthesis
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A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral ortho-C-H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso-protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
- Chen, Shuqing,Wang, Peng,Cheng, Hong-Gang,Yang, Chihui,Zhou, Qianghui
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p. 8384 - 8389
(2019/09/30)
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- Aromatic amine compound, EphB4 kinase inhibitor and its derivatives, and preparation methods thereof
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The invention provides an aromatic amine compound, an EphB4 kinase inhibitor and its derivatives, and preparation methods thereof. Aryl boronic acid or aryl boronate and O-benzoyl hydroxylamine compounds which are used as starting raw materials are stirred and reacted in an organic solvent at 30-100 DEG C in an air atmosphere under the action of a palladium catalyst, a norbornene derivative and analkali, and separation and purification are carried out after the reaction in order to obtain the aromatic amine compound. The method has the advantages of inexpensive and readily available raw materials, no halide ion residual after the completion of the reaction, and mild reaction conditions. The invention also provides the method for synthesizing the EphB4 kinase inhibitor and its derivatives.The EphB4 kinase inhibitor and its derivatives can be synthesized from the synthesized 3,5-diminated halogenobenzene or halogenoid benzene only through a simple step.
- -
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Paragraph 0064-0066
(2019/11/04)
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- Redox-Neutral ortho Functionalization of Aryl Boroxines via Palladium/Norbornene Cooperative Catalysis
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Palladium/norbornene (Pd/NBE) cooperative catalysis, also known as the Catellani reaction, has become an increasingly useful method for site-selective arene functionalization; however, certain constraints still exist because of its intrinsic mechanistic pathway. Herein, we report a redox-neutral ortho functionalization of aryl boroxines via Pd/NBE catalysis. An electrophile, such as carboxylic acid anhydrides or O-benzoyl hydroxylamines, is coupled at the boroxine ortho position, and a proton as the second electrophile is introduced at the ipso position. This reaction does not require extra oxidants or reductants and avoids stoichiometric bases or acids, thereby tolerating a wide range of functional groups. In particular, orthogonal chemoselectivity between aryl iodide and boroxine moieties is demonstrated, which could be used to control reaction sequences. Finally, a deuterium-labeling study supports the ipso protonation pathway. This unique mechanistic feature could inspire the development of a new class of Pd/NBE-catalyzed transformations.Poly-substituted aromatics are ubiquitously found in drugs and agrochemicals. To realize streamlined synthesis, it is highly attractive if functional groups can be site-selectively introduced at unactivated positions with common arene starting materials. Here, a method is developed to directly introduce acyl and amino groups at unactivated ortho positions of readily available aryl boron compounds. Compared with the known ortho functionalization approaches, this method does not require stoichiometric bases, external oxidants, or reductants. Consequently, the reaction is chemoselective: a wide range of functional groups, including highly reactive aryl iodides, can be tolerated. The primary innovation lies in the use of a proton to terminate the ipso aryl intermediate and regenerate the active palladium catalyst. This unique mode of reactivity in the palladium/norbornene catalysis should open the door for developing new redox-neutral methods for site-selective arene functionalization.A redox-neutral ortho functionalization of aryl boroxines via palladium/norbornene cooperative catalysis is developed. The ortho amination and acylation are achieved with carboxylic acid anhydrides and O-benzoyl hydroxylamines as an electrophile, respectively, whereas protonation occurs at the ipso position. This transformation avoids using either extra oxidants and reductants or stoichiometric bases and acids. In addition, orthogonal chemoselectivity between aryl iodide and boroxine moieties is demonstrated for pathway divergence.
- Li, Renhe,Liu, Feipeng,Dong, Guangbin
-
supporting information
p. 929 - 939
(2019/04/10)
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- [Pd(IPr*R)(acac)Cl]: Efficient bulky Pd-NHC catalyst for Buchwald-Hartwig C-N cross-coupling reaction
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A series of bulky palladium catalysts based on N-heterocyclic carbene, (Pd(NHC)(acac)Cl: NHC = IPr*me = N,N′-bis(2,6-bis(di-p-tolylmethyl)-4-methylphenyl)-imidazol-2 -ylidene, Pd(IPr*me)(acac)Cl; NHC = IPr*ipr = N,N′-bis(2,6-bis(di-4-isopropylphenyl)-4-methylphenyl)-imidazol-2 -ylidene, Pd(IPr*ipr)(acac)Cl; and NHC = IPr*tBu = N,N′-bis(2,6-bis(di-4-(tert-butyl)phenyl)- 4-methylphenyl)- imidazol-2-ylidene, Pd(IPr*tBu)(acac)Cl; acac = acetylacetonate), have been designed and synthesized. These three new catalysts showed much better catalytic activity in the Buchwald?Hartwig arylamination coupling reaction as compare to the earlier congener (IPr*)Pd(acac)Cl (IPr* = N,N′-bis(2,6-diphenylmethyl)-4-methylphenylimidazol-2-ylidene). The highly active PdII precatalyst [Pd(IPr*me)(acac)Cl] has been fully explored by using a wide range of substrates with different electronic and steric demands of coupling partners, for which up to 99% isolated yields were obtained. Remarkably, the moderate isolated yield was obtained for the challenging coupling of the amine bearing very bulky groups.
- Tian, Xiabing,Lin, Jing,Zou, Sheng,Lv, Junwei,Huang, Qingfei,Zhu, Jin,Huang, Shuping,Wang, Qiwei
-
supporting information
p. 125 - 130
(2018/03/06)
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- Three-Component Reactions of Arynes, Amines, and Nucleophiles via a One-Pot Process
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An unprecedented three-component reaction of arynes, tertiary amines, and nucleophiles has been demonstrated through ammonium salt intermediates. This protocol allows access to tertiary aniline derivatives containing the piperazine motif in good-to-excell
- Min, Gyoungwook,Seo, Jeongseob,Ko, Haye Min
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p. 8417 - 8425
(2018/07/15)
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- Potassium tert-butoxide-mediated generation of arynes from o-bromoacetophenone derivatives
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o-bromoacetophenone derivatives as new versatile aryne precursors are induced to selectively eliminate the CAr–Br and CAr–C(Ac) bonds in the help of t-BuOK. Furthermore, the active aryne intermediates are successfully appl
- Chang, Denghu,Gao, Fei,Shi, Lei
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p. 2428 - 2434
(2018/04/24)
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- Synergistic Ligand Effect between N-Heterocyclic Carbene (NHC) and Bicyclic Phosphoramidite (Briphos) Ligands in Pd-Catalyzed Amination
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A synergistic ligand effect between NHC and phosphorus ligands in Pd-catalyzed Buchwald-Hartwig amination reactions was demonstrated with tunable π-acceptor bicyclic bridgehead phosphoramidite (briphos) ligands. The catalytic activity of NHC-Pd-L (L = phosphorus ligand) precatalysts depends on the electronic properties of L. A NHC-Pd-L catalyst with an N-cyclohexyl-substituted briphos ligand was found to be highly efficient. A series of C-N bond coupling reactions between primary or secondary amines and aryl chlorides were performed with high yields under mild reaction conditions.
- Kim, Miji,Shin, Taeil,Lee, Ansoo,Kim, Hyunwoo
-
supporting information
p. 3253 - 3258
(2018/10/02)
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- Synthesis of Arylamines via Non-Aerobic Dehydrogenation Using a Palladium/Carbon-Ethylene System
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The reaction of cyclohexanones with amines proceeded under an ethylene atmosphere in the presence of a catalytic amount of palladium/carbon to afford a variety of arylamines in good to high yields. The present reaction was carried out under completely non-aerobic conditions, and which is in contrast with the previously reported aerobic system. has wide applicability affording a variety of aromatic amines, and co-product of the reaction is only gaseous ethane. Thus, this method is environmentally friendly. This protocol was applied intramolecularly to provide a novel method for the construction of quinoline and isoquinoline compounds. (Figure presented.).
- Shimomoto, Yuya,Matsubara, Ryosuke,Hayashi, Masahiko
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supporting information
p. 3297 - 3305
(2018/08/07)
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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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- Application of a 2-aryl indenylphosphine ligand in the Buchwald-Hartwig cross-coupling reactions of aryl and heteroaryl chlorides under the solvent-free and aqueous conditions
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An efficient solvent-free protocol for the Buchwald-Hartwig cross-coupling reaction of aryl and heteroaryl chlorides with primary and secondary amines using the Pd(dba)2/ligand 1 catalytic system has been developed. Notably, the catalytic system also efficiently catalyzed the reaction under aqueous conditions.
- Liu, Yan,Yuan, Jia,Wang, Zi-Fei,Zeng, Si-Hao,Gao, Meng-Yue,Ruan, Mei-Lin,Chen, Jian,Yu, Guang-Ao
-
supporting information
p. 5805 - 5810
(2017/07/22)
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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.
- -
-
Paragraph 0138; 0139
(2017/07/22)
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- Metal-free Synthesis of Aryl Amines: Beyond Nucleophilic Aromatic Substitution
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A mild and metal-free approach to C?N coupling is described that employs diaryliodonium salt electrophiles and secondary aliphatic amine nucleophiles. This reaction results in direct ipso-substitution of the iodonium moiety and unsymmetrical aryl(TMP)iodonium salts are primarily employed. Moreover, arene substituents and substitution patterns that currently pose a challenge to classical metal-free methods are accommodated and the alicyclic amine nucleophiles used here are unprecedented in other contemporary metal-free C?N coupling reactions.
- Sandtorv, Alexander H.,Stuart, David R.
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p. 15812 - 15815
(2016/12/16)
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- A Selective C?H Deprotonation Strategy to Access Functionalized Arynes by Using Hypervalent Iodine
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Described here is an efficient method to access highly functionalized arynes from unsymmetrical aryl(mesityl)iodonium tosylate salts. The iodonium salts are prepared in a single pot from either commercially available aryl iodides or arylboronic acids. The
- Sundalam, Sunil K.,Nilova, Aleksandra,Seidl, Thomas L.,Stuart, David R.
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p. 8431 - 8434
(2016/07/19)
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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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- 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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- A Bis(silylene)-Substituted ortho-Carborane as a Superior Ligand in the Nickel-Catalyzed Amination of Arenes
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The synthesis and structure of the first 1,2-bis(NHSi)-substituted ortho-carborane [(LSi:)C]2B10H10(termed SiCCSi) is reported (NHSi=N-heterocyclic silylene; L=PhC(NtBu)2). Its suitability to serve as a reliable bis(silylene) chelating ligand for transition metals is demonstrated by the formation of [SiCCSi]NiBr2and [SiCCSi]Ni(CO)2complexes. The CO stretching vibration modes of the latter indicate that the SiIIatoms in the SiCCSi ligand are even stronger σ donors than the PIIIatoms in phosphines and CIIatoms in N-heterocyclic carbene (NHC) ligands. Moreover, the strong donor character of the [SiCCSi] ligand enables [SiCCSi]NiBr2to act as an outstanding precatalyst (0.5 mol % loading) in the catalytic aminations of arenes, surpassing the activity of previously known molecular Ni-based precatalysts (1–10 mol %).
- Zhou, Yu-Peng,Raoufmoghaddam, Saeed,Szilvási, Tibor,Driess, Matthias
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supporting information
p. 12868 - 12872
(2016/10/04)
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- A quick Chan-Lam C-N and C-S cross coupling at room temperature in the presence of square pyramidal [Cu(DMAP)4I]I as a catalyst
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A rapid and efficient protocol for C-N and C-S cross coupling has been developed using a new square pyramidal copper complex, [Cu(DMAP)4I]I. The complex was successfully synthesized via a disproportionation reaction of CuI and DMAP in DMSO. The catalytic activity of the complex was found to be excellent for Chan-Lam coupling reaction between aryl boronic acid and amine, amide, azide or thiol. The reaction could be carried out in the presence of only 2 mol% of the copper catalyst in methanol at room temperature within a short time.
- Roy, Subhasish,Sarma, Manas Jyoti,Kashyap, Bishwapran,Phukan, Prodeep
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supporting information
p. 1170 - 1173
(2016/01/15)
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- Preparation method of novel bidentate phosphite ligand and application thereof in Buchwald-Hartwig reaction
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The invention discloses a preparation method of novel bidentate phosphite ligands and application thereof in Buchwald-Hartwig reaction and belongs to the field of organic synthetic chemistry. A series of novel bidentate phosphite ligands are synthesized by using 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxyl diphenyl and glycols with different structures as raw materials through a two-step one-pot method, are compounds very wide in application range and have the following structures. The novel preparation method has the advantages of being stable in structure, simple and convenient to synthesize, high in yield and easy to prepare in a large-scale mode. The ligands have higher reaction activity and substrate universality in the Pd catalyzed Buchwald-Hartwig reaction.
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-
Paragraph 0050; 0051; 0052; 0053; 0054; 0057; 0058; 0060-64
(2016/10/09)
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- Facile access to: N -substituted anilines via dehydrogenative aromatization catalysis over supported gold-palladium bimetallic nanoparticles
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N-Substituted anilines are widely utilized important compounds, and the development of their diverse synthetic procedures is of great significance. Herein, we have successfully developed a widely applicable powerful catalytic route to N-substituted anilines. In the presence of a gold-palladium alloy nanoparticle catalyst (Au-Pd/Al2O3) and styrene, various kinds of structurally diverse N-substituted anilines (twenty three examples) could be synthesized starting from cyclohexanones and amines (including aliphatic primary and secondary amines and anilines). The catalytic performance was strongly influenced by the nature of the catalyst. A supported gold catalyst (Au/Al2O3) was completely inactive for the present transformation. Although a supported palladium catalyst (Pd/Al2O3) gave the desired N-substituted anilines to some extent, the performance was inferior to that of Au-Pd/Al2O3. The catalytic activity of the palladium species in Au-Pd/Al2O3 was at least ca. three times higher than that in Pd/Al2O3. Moreover, the performance of Au-Pd/Al2O3 was superior to that of a physical mixture of Au/Al2O3 and Pd/Al2O3. Thus, palladium was intrinsically effective for the present transformation (dehydrogenative aromatization) and its performance was improved by alloying with gold. The present transformation proceeds through a sequence of the dehydrative condensation of cyclohexanones and amines to produce enamines (or ketimines), followed by the dehydrogenative aromatization to produce the corresponding N-substituted anilines. In the aromatization step, styrene could act as an effective hydrogen acceptor to selectively produce the desired N-substituted anilines without catalyzing the disproportionation of the enamine intermediates. The observed catalysis using Au-Pd/Al2O3 was truly heterogeneous in nature, and Au-Pd/Al2O3 could be reused.
- Taniguchi, Kento,Jin, Xiongjie,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 3929 - 3937
(2016/06/14)
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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
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supporting information
p. 2678 - 2682
(2015/04/27)
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- Nickel(II) complex incorporating methylene bridged tetradentate dicarbene ligand as an efficient catalyst toward CC and CN bond formation reactions
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For the evaluation of binding and catalytic nature of N-heterocyclic carbenes (NHCs) and their complexes, a new methylene bridged bis(aryloxy-NHC) ligand has been prepared. A novel air-stable Ni(II) complex bearing the new NHC ligand has been synthesized and characterized by elemental analysis, NMR (1H and 13C) as well as ESI-mass spectrometry. The molecular structure of the complex was identified by means of single crystal X-ray diffraction analysis which revealed that the Ni(II) complex possesses a square planar geometry with the ligand coordinating with bi-negative tetradentate C2O2 fashion and the complex showed efficient catalytic activity toward the Suzuki-Miyaura cross-coupling reaction between aryl halides and arylboronic acids under phosphine free conditions. The new complex 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. Both secondary and primary amines are well tolerated under the optimal reaction conditions.
- Nirmala, Muthukumaran,Prakash, Govindan,Ramachandran, Rangasamy,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz,Linert, Wolfgang
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- 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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- 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
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supporting information
p. 1587 - 1593
(2014/05/06)
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- Efficient C-N and C-S bond formation using the highly active [Ni(allyl)Cl(IPr*OMe)] precatalyst
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Two new [Ni(allyl)Cl(NHC)] complexes with the bulky yet flexible N-heterocyclic carbene (NHC) ligands IPr* {N,N'-bis[2,6- bis(diphenylmethyl)-4-methylphenyl]imidazole-2-ylidene} and IPr* OMe {N,N'-bis[2,6-bis(diphenylmethyl)-4-methoxyphenyl]imidazol-2- ylidene} are reported. These complexes were employed in the amination and sulfination of aryl halide species and were shown to perform well in these reactions, which typically required less than half as much catalyst as previous state-of-the-art nickel complexes. Copyright
- Martin, Anthony R.,Nelson, David J.,Meiries, Sebastien,Slawin, Alexandra M.Z.,Nolan, Steven P.
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supporting information
p. 3127 - 3131
(2014/06/09)
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- Coupling of boronic acids with amines in the presence of a supported copper catalyst
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An efficient heterogeneous catalytic method was developed for Chan-Lam reaction, coupling of amines and boronic acid. Copper on 4 A molecular sieve provided yields comparable to the methods published. The method provides the main advantages of a heterogeneous catalytic procedure, the preparation of the catalyst is easy, the workup of the reaction mixture is simple. Graphical abstract: [Figure not available: see fulltext.]
- Debreczeni, Nora,Fodor, Anna,Hell, Zoltan
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p. 1547 - 1551,5
(2014/11/12)
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- Ortho vs ipso: Site-selective pd and norbornene-catalyzed arene c-h amination using aryl halides
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A Pd and norbornene-catalyzed ortho-arene amination via Catellani-type C-H functionalization is reported. Aryl halides are used as substrates; N-benzoyloxyamines and isopropanol are employed as the amine source (oxidant) and reductant respectively. Exampl
- Dong, Zhe,Dong, Guangbin
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supporting information
p. 18350 - 18353
(2014/01/06)
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- Copper-catalyzed aerobic oxidative amination of arylboronic acid with aminal under base-free conditions
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A new process involving copper-catalyzed oxidative amination reaction of various arylboronic acids with aminals under mild conditions has been developed. The key copper-amide species involved in the C-N bond-forming process was generated via C-N bond cleavage of aminal under base-free conditions. Moderate yields of desired amination products can be obtained under mild conditions when air was served as oxidant and PhCO2H was used as an additive.
- Zhou, Yanping,Xie, Yinjun,Yang, Lei,Xie, Pan,Huang, Hanmin
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supporting information
p. 2713 - 2716
(2013/06/05)
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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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- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
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We report herein that amides are excellent N-sources in the NHC-Pd(II)-Im complex 1 catalyzed amination of aryl chlorides. In the presence of KO tBu, various aryl chlorides and amides can react smoothly to give the corresponding aminated products in moderate to almost quantitative yields at room temperature within 6 h.
- Chen, Wen-Xin,Shao, Li-Xiong
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p. 9236 - 9239,4
(2012/12/12)
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- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
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We report herein that amides are excellent N-sources in the NHC-Pd(II)-Im complex 1 catalyzed amination of aryl chlorides. In the presence of KO tBu, various aryl chlorides and amides can react smoothly to give the corresponding aminated products in moderate to almost quantitative yields at room temperature within 6 h.
- Chen, Wen-Xin,Shao, Li-Xiong
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p. 9236 - 9239
(2013/01/15)
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- Nickel-catalyzed amination of aryl sulfamates and carbamates using an air-stable precatalyst
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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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- 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; 49
(2012/07/27)
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- NOVEL CATALYSTS
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The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.
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Page/Page column 68-69
(2012/06/01)
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- Nickel-catalyzed amination of aryl phosphates through cleaving aryl C-O bonds
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The amination of triaryl phosphates was achieved using a Ni(II)-(σ-Aryl) complex/NHC catalyst system in dioxane at 110 °C in the presence of NaH as base. Electron-neutral, -rich, and -deficient triaryl phosphates were coupled with a wider range of amine partners including cyclic and acyclic secondary amines, aliphatic primary amines, and anilines in good to excellent yields.
- Huang, Jin-Hua,Yang, Lian-Ming
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p. 3750 - 3753
(2011/09/14)
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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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supporting information; experimental part
p. 2171 - 2173
(2011/04/25)
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- Room-temperature nickel-catalyzed amination of heteroaryl/aryl chlorides with Ni(II)-(σ-Aryl) complex as precatalyst
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The room-temperature cross-coupling of heteroaryl and aryl chlorides with secondary cyclic amines can be effected using Ni(II)-(σ-aryl) complex as pre-catalyst. Some useful aromatic and heteroaromatic amine derivatives were readily synthesized in moderate to good yields in the presence of the Ni(II)-(σ-aryl) complex/NHC/KOtBu/toluene system.
- Fan, Xin-Heng,Li, Gang,Yang, Lian-Ming
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experimental part
p. 2482 - 2484
(2011/07/07)
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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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- Well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complexes catalyzed amination of aryl chlorides
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A new class of well-defined NHC-Pd(II)-Im complexes was synthesized and was found to be an efficient catalyst for the amination reactions of aryl chlorides. Under the optimal reaction conditions, a range of amines can be coupled to give the amination products in good to high yields.
- Zhu, Lei,Gao, Ting-Ting,Shao, Li-Xiong
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experimental part
p. 5150 - 5155
(2011/07/31)
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- Examination of the aromatic amination catalyzed by palladium on charcoal
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The Buchwald-Hartwig amination of aryl halides with secondary amines and functionalized aromatic amines catalyzed by solid-supported palladium is reported. The choices of ligand, base and solvent are crucial for the successful coupling. The ami-nation of aromatic iodides, bromides and chlorides can be easily achieved with palladium on charcoal in the presence of a biphenylphosphane-type ligand at 80-110 °C. In addition, the palladium on charcoal catalyst is easily separable after the reaction, and reusable several times with only small activity loss.
- Komaromi, Anna,Novak, Zoltan
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supporting information; experimental part
p. 1523 - 1532
(2010/08/19)
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- Ligand-free iron/copper cocatalyzed N-arylations of aryl halides with amines under microwave irradiation
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Ligand-free iron/copper cocatalyzed cross-coupling reactions of aryl halides with amines were carried out to provide the corresponding coupling products in good yields. It is worth noting that the method displays a broad substrate scope, and is convenient, rapid, low-cost and environmentally friendly.
- Guo, Diliang,Huang, He,Zhou, Yu,Xu, Jinyi,Jiang, Hualiang,Chen, Kaixian,Liu, Hong
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supporting information; experimental part
p. 276 - 281
(2011/02/28)
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