- Product selective reaction controlled by the combination of palladium nanoparticles, continuous microwave irradiation, and a co-existing solid; ligand-free Buchwald-Hartwig aminationvs.aryne amination
-
We have developed a continuous microwave irradiation-assisted Buchwald-Hartwig amination using our original Pd nanoparticle catalyst with a copper plate as a co-existing metal solid. In this methodology, a microwave-controlled product selectivity was achieved between Buchwald-Hartwig amination and aryne amination performed under strongly basic conditions and at a high reaction temperature, because a polar chemical species such as Ar-Pd-halogen might be activated selectively by microwave radiation. Moreover, our catalyst could be used repeatedly over 10 times, and the amount of Pd leaching could be suppressed to a low level.
- Akiyama, Toshiki,Arai, Masayoshi,Arisawa, Mitsuhiro,Haneoka, Hitoshi,Harada, Kazuo,Murai, Kenichi,Murakami, Yosuke,Ohki, Yuuta,Ohta, Ryousuke,Sako, Makoto,Sirimangkalakitti, Natchanun,Suzuki, Takeyuki,Takahashi, Naoyuki,Takehara, Tsunayoshi,Yamada, Makito
-
supporting information
p. 8131 - 8137
(2021/10/29)
-
- 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
-
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
-
-
- Amination of Aryl Halides Mediated by Electrogenerated Nickel from Sacrificial Anode
-
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)
-
- Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling
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The coupling of transition-metal to photoredox catalytic cycles through single-electron transfer steps has become a powerful tool in the development of catalytic processes. In this work, we demonstrated that transition-metal catalysis can be coupled to al
- Bortnikov, Evgeniy O.,Semenov, Sergey N.
-
supporting information
p. 782 - 793
(2020/12/01)
-
- Photo-induced dealdehyding method
-
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; 0096-0101
(2020/06/16)
-
- Copper-Catalyzed Electrophilic Amination of Alkoxyarylsilanes
-
We report a copper-catalyzed amination reaction between simple alkoxyarylsilanes and N-benzoyloxyamines. Silver fluoride serves as a stoichiometric base as well as an indispensable activator that allows the catalytic process to proceed. Multiply alkoxylated arylsilanes, such as trialkoxyarylsilanes and dialkoxyarylsilanes were transformed into the corresponding tertiary anilines under mild reaction conditions.
- Hitoshio, Kenshiro,Saito, Hayate,Shimokawa, Jun,Yorimitsu, Hideki,Zhang, Qian
-
supporting information
(2020/07/04)
-
- Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
-
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
-
supporting information
p. 3421 - 3426
(2020/06/25)
-
- Ru(II)-Catalyzed Amination of Aryl Fluorides via η6-Coordination
-
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
-
supporting information
p. 3706 - 3711
(2020/03/11)
-
- Transition-Metal-Catalyzed Amination of Aryl Fluorides
-
Arene activation via transition-metal (TM) η 6-coordination has merged as a powerful method to diversify the aromatic C-F bond, which is relatively less reactive due to its high bond energy. However, this strategy in general requires to use largely excess arenes or TM η 6-complexes as the substrates. Herein, we highlight our recent work on the catalytic S NAr amination of electron-rich and electron-neutral aryl fluorides that are inert in classical S NAr reactions. This protocol enabled by a Ru/hemilabile ligand catalyst covers a broad scope of substrates without wasting arenes. Mechanistic studies revealed that the nucleo?-philic substitution proceeded on a Ru η 6-arene complex, and the hemilabile ligand significant promoted the arene dissociation.
- Kang, Qi-Kai,Li, Yuntong,Lin, Yunzhi,Shi, Hang
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p. 1235 - 1239
(2020/07/20)
-
- Pyrazolyl bistriazolyl phosphine compound and application of pyrazolyl bistriazolyl phosphine compound
-
The invention discloses a pyrazolyl bistriazolyl phosphine compound and application thereof. The invention discloses a compound shown as a formula I. In the formula I, R1 is hydrogen, C1-C6 alkyl or phenyl; R2 and R3 are phenyl; R4 and R5 are independently a C1-C6 alkyl group, a C3-C8 cycloalkyl group, or a phenyl group. The pyrazolyl bistriazolyl phosphine compound disclosed by the invention is stable in property, excellent in catalytic effect and high in selectivity, and can be applied to catalytic coupling of amine, boric acid compounds and halides.
- -
-
Paragraph 0237-0240
(2020/07/24)
-
- Preparation method of pyrazole bistriazolylphosphine compound
-
The invention discloses a preparation method of a pyrazole bistriazolylphosphine compound. The invention discloses a preparation method of a compound as shown in a formula I. The preparation method comprises the following step: under the action of an alkali, carrying out a phosphonation reaction process as shown in the specification on a compound as shown in a formula II and a compound as shown ina formula III in a solvent in the presence of protective gas to obtain the compound as shown in the formula I, wherein R1 is hydrogen, a C1-C6 alkyl group or a phenyl group, R2 and R3 are phenyl, R4and R5 are independently a C1-C6 alkyl group, a C3-C8 cycloalkyl group or a phenyl group and x is halogen. The pyrazolyl bistriazolylphosphine compound obtained by the preparation method disclosed bythe invention is stable in property, excellent in catalytic effect and high in selectivity, and can be applied to catalytic coupling of amine, boric acid compounds and halides.
- -
-
Paragraph 0235-0238
(2020/05/30)
-
- METHODS FOR FORMING ARYL CARBON-NITROGEN BONDS USING LIGHT AND PHOTOREACTORS USEFUL FOR CONDUCTING SUCH REACTIONS
-
The disclosure relates to a method for forming aryl carbon-nitrogen bonds and to photoreactors useful in these and other light-driven reactions. The method comprises contacting an aryl halide with an amine in the presence of a Ni salt catalyst solution and an optional base, thereby forming a reaction mixture; exposing the reaction mixture to light under reaction condition sufficient to produce the aryl carbon-nitrogen bonds. In certain embodiments, the amine may be present in a molar excess to the aryl halide. In certain embodiments, the Ni salt catalyst solution includes a Ni(II) salt and a polar solvent, wherein the Ni(II) salt is dissolved in the polar solvent. In certain embodiments, the reactions conditions include holding the reaction mixture at between about room temperature and about 80° C. for between about 1 hour and about 20 hours such that at least about 50% yield is obtained.
- -
-
Paragraph 0097-0098; 0168-0169
(2019/11/22)
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- Redox-neutral: Ortho -C-H amination of pinacol arylborates via palladium(ii)/norbornene catalysis for aniline synthesis
-
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.
- -
-
Paragraph 0076-0078
(2019/11/04)
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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
-
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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- Three-Component Reactions of Arynes, Amines, and Nucleophiles via a One-Pot Process
-
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)
-
- Modular ipso/ ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene Cooperative Catalysis
-
Palladium/norbornene (Pd/NBE) cooperative catalysis has emerged as a useful tool for preparing poly substituted arenes; however, its substrate scope has been largely restricted to aryl iodides. While aryl bromides are considered as standard substrates for Pd-catalyzed cross coupling reactions, their use in Pd/NBE catalysis remains elusive. Here we describe the development of general approaches for aryl bromide-mediated Pd/NBE cooperative catalysis. Through careful tuning the phosphine ligands and quenching nucleophiles, ortho amination, acylation and alkylation of aryl bromides have been realized in good efficiency. Importantly, various heteroarene substrates also work well and a wide range of functional groups are tolerated. In addition, the utility of these methods has been demonstrated in sequential cross coupling/ortho functionalization reactions, consecutive Pd/NBE-catalyzed difunctionalization to construct penta-substituted aromatics and two-step meta functionalization reactions. Moreover, the origin of the ligand effect in ortho amination reactions has been explored through DFT studies. It is expected that this effort would significantly expand the reaction scope and enhance the synthetic potential for Pd/NBE catalysis in preparing complex aromatic compounds.
- Dong, Zhe,Lu, Gang,Wang, Jianchun,Liu, Peng,Dong, Guangbin
-
supporting information
p. 8551 - 8562
(2018/06/25)
-
- [Pd(IPr*R)(acac)Cl]: Efficient bulky Pd-NHC catalyst for Buchwald-Hartwig C-N cross-coupling reaction
-
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)
-
- C-N Cross-Coupling via Photoexcitation of Nickel-Amine Complexes
-
C-N cross-coupling is an important class of reactions with far-reaching impacts across chemistry, materials science, biology, and medicine. Transition metal complexes can elegantly orchestrate diverse aminations but typically require demanding reaction conditions, precious metal catalysts, or oxygen-sensitive procedures. Here, we introduce a mild nickel-catalyzed C-N cross-coupling methodology that operates at room temperature using an inexpensive nickel source (NiBr2·3H2O), is oxygen tolerant, and proceeds through direct irradiation of the nickel-amine complex. This operationally robust process was employed for the synthesis of diverse C-N-coupled products (40 examples) by irradiating a solution containing an amine, an aryl halide, and a catalytic amount of NiBr2·3H2O with a commercially available 365 nm LED at room temperature without added photoredox catalyst and the amine substrate serving additional roles as the ligands and base. Density functional theory calculations and kinetic isotope effect experiments were performed to elucidate the observed C-N cross-coupling reactivity.
- Lim, Chern-Hooi,Kudisch, Max,Liu, Bin,Miyake, Garret M.
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supporting information
p. 7667 - 7673
(2018/05/31)
-
- ARYLATION OF ALIPHATIC AMINES
-
The invention relates to a method for arylation of amines, such as aliphatic amines by reaction of aryl-halogens, e.g. chloro- or fluorobenzene derivatives without strongly electron withdrawing substituents in the presence of a strong base.
- -
-
Page/Page column 24; 26
(2017/09/07)
-
- Synthesis of N-heterocyclic carbene-Pd(II) complexes and their catalytic activity in the Buchwald-Hartwig amination of aryl chlorides
-
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
-
p. 7308 - 7314
(2017/12/01)
-
- N-heterocyclic carbene-palladium complex, and preparation method and application thereof
-
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)
-
- Evaluating 1,1′-Bis(phosphino)ferrocene Ancillary Ligand Variants in the Nickel-Catalyzed C-N Cross-Coupling of (Hetero)aryl Chlorides
-
Previous reports in the literature have established the utility of 1,1′-bis(diphenylphosphino)ferrocene (DPPF, LPh) in the nickel-catalyzed cross-coupling of (hetero)aryl electrophiles with primary or secondary amines. In an effort to evaluate
- Clark, Jillian S. K.,Voth, Christopher N.,Ferguson, Michael J.,Stradiotto, Mark
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supporting information
p. 679 - 686
(2017/04/21)
-
- n-Butyllithium-mediated synthesis of N-aryl tertiary amines by reactions of fluoroarenes with secondary amines at room temperature
-
A simple and facile method for the synthesis of aromatic tertiary amines by amination of fluoroarenes with secondary amines in the presence of n-butyllithium at room temperature was reported.
- Lin, Yingyin,Li, Meng,Ji, Xinfei,Wu, Jingjing,Cao, Song
-
p. 1466 - 1472
(2017/02/18)
-
- Organonickel complexes encumbering bis-imidazolylidene carbene ligands: Synthesis, X-ray structure and catalytic insights on Buchwald-Hartwig amination reactions
-
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)
-
- Mechanism and Scope of Base-Controlled Catalyst-Free N-Arylation of Amines with Unactivated Fluorobenzenes
-
A general method for transition metal-free N-arylation of amines has been developed. Mechanistic studies have revealed that the ability of the base to facilitate the desired amination without promoting unwanted side reactions is the guiding factor. By employing lithium bis(trimethylsilyl)amide as a base the resultant deprotonated amines readily react with a range of unactivated fluorobenzene derivatives. This new arylation method is utilized for the simple two-step synthesis of the antidepressant Vortioxetine.
- Borch Jacobsen, Christian,Meldal, Morten,Diness, Frederik
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supporting information
p. 846 - 851
(2017/02/05)
-
- An easily available N-heterocyclic carbene–palladium(II) catalyst for Buchwald–Hartwig amination of aryl chlorides
-
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)
-
- 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
-
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
-
p. 24484 - 24490
(2016/03/15)
-
- Synthesis of N-heterocyclic carbene-PdCl2-(iso)quinoline complexes and their application in arylamination at low catalyst loadings
-
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)
-
- Nickel(II) complex incorporating methylene bridged tetradentate dicarbene ligand as an efficient catalyst toward CC and CN bond formation reactions
-
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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-
- Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O -Benzoyl Hydroxylamines
-
A copper-catalyzed electrophilic amination of aryl and heteroaryl aluminums with N,N-dialkyl-O-benzoyl hydroxylamines that affords the corresponding anilines in good yields has been developed. The catalytic reaction proceeds very smoothly under mild conditions and exhibits good substrate scope. Moreover, the developed catalytic system is also well suited for heteroaryl aluminum nucleophiles, providing facile access to heteroaryl amines.
- Zhou, Shuangliu,Yang, Zhiyong,Chen, Xu,Li, Yimei,Zhang, Lijun,Fang, Hong,Wang, Wei,Zhu, Xiancui,Wang, Shaowu
-
p. 6323 - 6328
(2015/06/30)
-
- N-(1-Oxy-2-picolyl)oxalamic Acid as an Efficient Ligand for Copper-Catalyzed Amination of Aryl Iodides at Room Temperature
-
N-(1-Oxy-pyridin-2-ylmethyl)oxalamic acid was identified as efficient ligand for CuI-catalyzed amination of aryl halides at room temperature. In our catalytic system, N-arylation of cyclic secondary amines, primary amines, amino acids, and ammonia proceeded with moderate to excellent yields and high functional group tolerance.
- Wang, Yongbin,Ling, Jing,Zhang, Yu,Zhang, Ao,Yao, Qizheng
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p. 4153 - 4161
(2015/07/01)
-
- Two cadmium(II) complexes with oxazoline-based ligands as effective catalysts for C-N cross-coupling reactions
-
Binuclear [{(DMOX)CdCl}2(μ-Cl)2] (DMOX = 4,5-dihydro-2-(4,5-dihydro-4,4-dimethyloxazol-2-yl)-4,4-dimethyl-oxazole) (1) and mononuclear [(Dm-Pybox)CdCl2] (Dm-Pybox = 2,6-bis[4′,4′-dimethyloxazolin-2′-yl]pyridine) (2) were obtained by reacting CdCl2 with DMOX and Dm-Pybox ligands, respectively. In the solid state, the supramolecular structures of 1 and 2 feature helical chains fabricated by C-H-Cl hydrogen bond interactions. The C-N cross-coupling reactions catalyzed by the two complexes were also investigated in homogeneous system. The results show that binuclear complex 1 exhibit significantly enhanced catalytic activity for C-N cross-coupling reactions.
- Jia, Wei-Guo,Li, Dan-Dan,Gu, Cuiping,Dai, Yuan-Chen,Zhou, Ying-Hua,Yuan, Guozan,Sheng, En-Hong
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p. 226 - 231
(2015/02/05)
-
- Can Palladium Acetate Lose Its "saltiness"? Catalytic Activities of the Impurities in Palladium Acetate
-
Commercially available palladium acetate often contains two major impurities, whose presence can impact the overall catalytic efficacy. This systematic study provides a comparison of the differences in catalytic activity of pure palladium acetate, Pd3(OAc)6, with the two impurities: Pd3(OAc)5(NO2) and polymeric [Pd(OAc)2]n in a variety of cross-coupling reactions. The solid state 13C NMR spectra of all three compounds in conjunction with DFT calculations confirm their reported geometries.
- Carole, William A.,Bradley, Jonathan,Sarwar, Misbah,Colacot, Thomas J.
-
supporting information
p. 5472 - 5475
(2015/11/18)
-
- N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole complexes: Synthesis and catalytic activity toward amination of aryl chlorides
-
A series of novel N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole (NHC-PdII-Ox) complexes 3 were successfully synthesized from commercially available imidazolium salts 1, PdCl2, and 4,5-dihydrooxazoles 2 in a one-step process, and these complexes showed efficient catalytic activity toward the amination of aryl chlorides. Both secondary and primary amines were tolerated under the same reaction conditions. Under the optimal reaction conditions, the expected coupling products were obtained in moderate to high yields.
- Huang, Pei,Wang, Yi-Xiang,Yu, Hong-Fei,Lu, Jian-Mei
-
supporting information
p. 1587 - 1593
(2014/05/06)
-
- Nickel-catalyzed cross-coupling of aryltrimethylammonium triflates and amines
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Nickel-catalyzed cross-coupling of aryltrimethylammonium triflates and amines was carried out under mild conditions. The reaction has a broad scope of substrates and can be performed by a one-pot procedure from an aryldimethylamine.
- Zhang, Xue-Qi,Wang, Zhong-Xia
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p. 1448 - 1453
(2014/03/21)
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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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- Nickel-catalyzed coupling of fluoroarenes and amines
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The combination of bis(cyclooctadiene)nickel [Ni(COD)2] and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene hydrochloride (IPr×HCl) effectively catalyzes coupling of fluoroarenes with amines in the presence of sodium tert-butoxide (t-BuONa). A
- Zhu, Feng,Wang, Zhong-Xia
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p. 3694 - 3702
(2014/01/06)
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- A robustness screen for the rapid assessment of chemical reactions
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In contrast to the rapidity with which scientific information is published, the application of new knowledge often remains slow, and we believe this to be particularly true of newly developed synthetic organic chemistry methodology. Consequently, methods to assess and identify robust chemical reactions are desirable, and would directly facilitate the application of newly reported synthetic methodology to complex synthetic problems. Here, we describe a simple process for assessing the likely scope and limitations of a chemical reaction beyond the idealized reaction conditions initially reported. Using simple methods and common analytical techniques we demonstrate a rapid assessment of an established chemical reaction, and also propose a simplified analysis that may be reported alongside new synthetic methodology.
- Collins, Karl D.,Glorius, Frank
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p. 597 - 601
(2013/07/26)
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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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- Transition-metal-free electrophilic amination of arylboroxines
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A transition-metal-free strategy to construct C(sp2)-N bonds using arylboroxines and O-benzoyl hydroxylamines as coupling partners has been developed. This transformation provides a useful method to access various aromatic amines.
- Xiao, Qing,Tian, Leiming,Tan, Renchang,Xia, Ying,Qiu, Di,Zhang, Yan,Wang, Jianbo
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experimental part
p. 4230 - 4233
(2012/09/22)
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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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- 2,6-diisopropoxyphenyl(dicyclohexyl)phosphine: A new ligand for palladium-catalyzed amination reactions of aryl chlorides with potassium hydroxide as the base
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A new, readily available monophosphine tetrafluoroborate salt [L2·HBF4] was developed for the palladium-catalyzed amination reaction of aryl chlorides in moderate to high yields with the cheap and easily available potassium hydroxide as the base. The reaction enjoys a wide scope, lower reaction temperatures, shorter reaction times, high yields, and low catalyst loading when compared to some of same amination reactions reported in the literature. Based on a kinetic study, 31P NMR measurements, and DFT calculations, a mechanism involving a 1:1 Pd/L species is proposed.
- Lue, Bo,Li, Pengbin,Fu, Chunling,Xue, Liqin,Lin, Zhenyang,Ma, Shengming
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experimental part
p. 100 - 112
(2011/04/12)
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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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supporting information; experimental part
p. 3750 - 3753
(2011/09/14)
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- Manganese-catalyzed cross-coupling reactions of aliphatic amines with aryl halides
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An efficient and convenient protocol has been developed for the N-arylation of aliphatic amines with differently substituted aryl halides using a MnCl2·4H2O/l-proline catalyst and NaOt-Bu as the base in DMSO.
- Yong, Fui-Fong,Teo, Yong-Chua
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supporting information; experimental part
p. 3910 - 3912
(2010/08/20)
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- Catalytic SNAr reaction of non-activated fluoroarenes with amines via Ru η6-arene complexes
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Ru-catalyzed SNAr reaction of non-activated fluoroarenes with secondary amines proceeded through η6-arene complexes to give aminated products in up to 79% yield.
- Otsuka, Maiko,Endo, Kohei,Shibata, Takanori
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supporting information; experimental part
p. 336 - 338
(2010/05/01)
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- Facile catalytic SNAr reaction of nonactivated fluoroarenes with amines using η6-benzene ruthenium(II) complex
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Catalytic SNAr reaction of fluoroarenes possessing no electron-withdrawing group(s) with cyclic amines was achieved using a readily accessible Ru catalyst, which was prepared from [Ru(benzene)Cl2] 2, AgOTf, and P(p-FC6H4)3. The coexistence of molecular sieves MS4A realized high conversion and various substituted aryl amines were obtained in good to high yields. Georg Thieme Verlag Stuttgart New York.
- Otsuka, Maiko,Yokoyama, Hiroya,Endo, Kohei,Shibata, Takanori
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scheme or table
p. 2601 - 2606
(2010/11/19)
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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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