- Aerobic iron-catalyzed site-selective C(sp3)–C(sp3) bond cleavage in N-heterocycles
-
The kinetic and thermodynamic stability of C(sp3)–C(sp3) bonds makes the site-selective activation of these motifs a real synthetic challenge. In view of this, herein a site-selective method of C(sp3)–C(sp3) bon
- Beller, Matthias,Junge, Kathrin,Leonard, David K.,Li, Wu,Rockstroh, Nils
-
-
- N-substituted aminobiphenyl palladacycles stabilized by dialkylterphenyl phosphanes: Preparation and applications in C[sbnd]N cross-coupling reactions
-
Neutral and cationic N-methyl- and N-phenyl-2-aminobiphenyl methanesulfonate palladacycles stabilized with dialkylterphenyl phosphanes have been prepared and characterized. Neutral structures are favored with the less bulky phosphane PMe2ArXyl2, L1, while more sterically demanding ligands PiPr2ArXyl2, L3, and PCyp2ArXyl2 (Cyp = cyclopentyl), L4, lead to cationic complexes in which the phosphane exhibits a bidentate κ1-P, η1-Carene coordination mode involving one of the ipso carbon atoms of a flanking terphenyl aryl ring. The complexes were evaluated for activity in C[sbnd]N cross-coupling reactions and [Pd(N-methyl-2-aminobiphenyl)L4](OMs) (OMs = mesylate) was identified as the most efficient precatalyst, facilitating the coupling of aryl chlorides with secondary and primary amines and indoles.
- Monti, Andrea,Rama, Raquel J.,Gómez, Beatriz,Maya, Celia,álvarez, Eleuterio,Carmona, Ernesto,Nicasio, M. Carmen
-
supporting information
(2021/01/19)
-
- NOVEL HETEROCYCLIC COMPOUNDS AS CDK8/19 INHIBITORS
-
The present invention relates to novel compounds of formula (I): or a pharmaceutically acceptable salt or stereoisomer thereof, which exhibit the properties of a CDK 8/19 inhibitor. The invention also relates to a pharmaceutical composition containing said compounds and to the use thereof as pharmaceutical drugs for treating diseases or disorders.
- -
-
Paragraph 0225
(2020/07/07)
-
- 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
-
p. 1235 - 1239
(2020/07/20)
-
- Dialkylterphenyl Phosphine-Based Palladium Precatalysts for Efficient Aryl Amination of N-Nucleophiles
-
A series of 2-aminobiphenyl palladacycles supported by dialkylterphenyl phosphines, PR2Ar′ (R=Me, Et, iPr, Cyp (cyclopentyl), Ar′=ArDipp2, ArXyl2f, Dipp (2,6-C6H3-(2,6-C6H3-(CHMe2)2)2), Xyl=xylyl) have been prepared and structurally characterized. Neutral palladacycles were obtained with less bulky terphenyl phosphines (i.e., Me and Et substituents) whereas the largest phosphines provided cationic palladacycles in which the phosphines adopted a bidentate hemilabile k1-P,η1-Carene coordination mode. The influence of the ligand structure on the catalytic performance of these Pd precatalysts was evaluated in aryl amination reactions. Cationic complexes bearing the phosphines PiPr2ArXyl2 and PCyp2ArXyl2 were the most active of the series. These precatalysts have demonstrated a high versatility and efficiency in the coupling of a variety of nitrogen nucleophiles, including secondary amines, alkyl amines, anilines, and indoles, with electronically deactivated and ortho-substituted aryl chlorides at low catalyst loadings (0.25–0.75 mol % Pd) and without excess ligand.
- Rama, Raquel J.,Maya, Celia,Nicasio, M. Carmen
-
supporting information
p. 1064 - 1073
(2020/01/25)
-
- Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application
-
Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.
- Sinai, ádám,Simkó, Dániel Cs.,Szabó, Fruzsina,Paczal, Attila,Gáti, Tamás,Bényei, Attila,Novák, Zoltán,Kotschy, András
-
supporting information
p. 1122 - 1128
(2020/03/03)
-
- Methyl-α-d-glucopyranoside as Green Ligand for Selective Copper-Catalyzed N-Arylation
-
In the selective N-arylation of amines or azoles with aryl halidesa-, methyl-α-d-glucopyranoside (MG) was found to function as a green ligand of copper powder. In addition, nitrogen heterocyclic amine compounds can also undergo the N-arylation coupling with heterocyclic aryl chlorides. This process allows access to a variety of aromatic amines and aryl azoles under mild reaction conditions, has good tolerance, and proceeds in moderate to high yield.
- Chen, Fengyang,Chen, Guoliang,Chen, Yuanguang,Du, Fangyu,Zhou, Qifan
-
p. 4590 - 4600
(2019/12/11)
-
- Practical Catalytic Cleavage of C(sp3)?C(sp3) Bonds in Amines
-
The selective cleavage of thermodynamically stable C(sp3)?C(sp3) single bonds is rare compared to their ubiquitous formation. Herein, we describe a general methodology for such transformations using homogeneous copper-based catalysts in the presence of air. The utility of this novel methodology is demonstrated for Cα?Cβ bond scission in >70 amines with excellent functional group tolerance. This transformation establishes tertiary amines as a general synthon for amides and provides valuable possibilities for their scalable functionalization in, for example, natural products and bioactive molecules.
- Li, Wu,Liu, Weiping,Leonard, David K.,Rabeah, Jabor,Junge, Kathrin,Brückner, Angelika,Beller, Matthias
-
supporting information
p. 10693 - 10697
(2019/07/09)
-
- PRMT5 INHIBITORS AND USES THEREOF
-
Described herein are compounds of Formula (I), pharmaceutically acceptable salts thereof, and pharmaceutical compositions thereof. Compounds of the present invention are useful for inhibiting PRMT5 activity. Methods of using the compounds for treating PRMT5-mediated disorders are also described.
- -
-
Paragraph 0368-0369
(2019/04/05)
-
- [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)
-
- 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)
-
- Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald-Hartwig Amination in Air
-
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
-
p. 2914 - 2925
(2017/03/23)
-
- The synthesis of planar chiral pseudo-gem aminophosphine pre-ligands based on [2.2]paracyclophane
-
The synthesis of three planar chiral pseudo-gem disubstituted [2.2]paracyclophane-derived P,N-pre-ligands is reported along with preliminary results of their activity in the amination of aryl bromides and chlorides. The pseudo-gem aminophosphines were capable of mediating the coupling reaction at a loading of 1 mol%.
- Jayasundera, Krishanthi P.,Engels, Tim G. W.,Lun, David J.,Mungalpara, Maulik N.,Plieger, Paul G.,Rowlands, Gareth J.
-
p. 8975 - 8984
(2017/11/09)
-
- Buttressing Effect as a Key Design Principle towards Highly Efficient Palladium/N-Heterocyclic Carbene Buchwald–Hartwig Amination Catalysts
-
The backbone substitution of the standard 1,3-bis(2,6-diisopropylphenyl)-2H-imidazol-2-ylidene (IPr) ligand by dimethylamino groups was previously shown to induce a dramatic improvement in the catalytic efficiency of the corresponding Pd–PEPPSI (pyridine-enhanced pre-catalyst preparation, stabilization, and initiation) pre-catalysts in N-arylation reactions. Herein, a thorough structure/activity study towards rationalizing this beneficial effect has been described. In addition to the previously reported IPr (Formula presented.) and IPr (Formula presented.) ligands, the new IPr (Formula presented.) and IPr (Formula presented.) ligands, which bear one bulkier diisopropylamino group and a combination of dimethylamino and chloro substituents, respectively, have been designed and analyzed in the study. The influence of the backbone substitution was found to be steric in origin and is related to the well-known buttressing effect encountered in arene chemistry. The usefulness and versatility of this approach was demonstrated through the development of a highly efficient catalytic system for the challenging arylation of bulky α,α,α-trisubstituted primary amines. The optimized system based on the [PdCl(η3-cinnamyl)(IPr (Formula presented.))] or [PdCl(η3-cinnamyl)(IPr (Formula presented.))] pre-catalysts operates under unprecedented mild conditions (catalyst loadings: 0.5–2 mol %, reaction temperatures: 40–60 °C) with a wide substrate scope.
- Zhang, Yin,Lavigne, Guy,Lugan, No?l,César, Vincent
-
p. 13792 - 13801
(2017/09/12)
-
- Solvent-Free Buchwald-Hartwig (Hetero)arylation of Anilines, Diarylamines, and Dialkylamines Mediated by Expanded-Ring N-Heterocyclic Carbene Palladium Complexes
-
A highly efficient solvent-free protocol for the Buchwald-Hartwig (hetero)arylation of anilines, diarylamines, and dialkylamines mediated by the expanded-ring N-heterocyclic carbene palladium complex (THP-Dipp)Pd(cinn)Cl [THP-Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; cinn = cinnamyl, 3-phenylallyl] was developed. The catalytic protocol was efficient for the coupling of amines and (hetero)aryl chlorides and bromides bearing donor, acceptor, and bulky substituents.
- Topchiy, Maxim A.,Dzhevakov, Pavel B.,Rubina, Margarita S.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
-
supporting information
p. 1908 - 1914
(2016/04/20)
-
- 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
-
p. 525 - 529
(2016/07/20)
-
- Water-soluble palladacycles containing hydroxymethyl groups: Synthesis, crystal structures and use as catalysts for amination and Suzuki coupling of reactions
-
Two water-soluble monophosphine [PPh3 and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl(Sphos)]-palladacycles containing hydroxymethyl groups 2-3 were prepared by cyclopalladation and chloride bridge-splitting reactions. The complexes were characterized by elemental analysis, ESI-MS and NMR. In addition, single-crystal X-ray analysis reveals that they have one-dimensional lamellar structures involving intermolecular hydrogen bonds and π-π interactions. The use of these palladacycles as catalysts for amination and Suzuki coupling of aryl chlorides in water was investigated. Complex 3 was found to be very efficient for these coupling reactions. Additionally, it was also successfully used in Suzuki coupling of (hydroxymethyl)phenylboronic acid for the synthesis of substituted 2-N-heterocyclic biarylmethanols.
- Han, Xin,Li, Hong-Mei,Xu, Chen,Xiao, Zhi-Qiang,Wang, Zhi-Qiang,Fu, Wei-Jun,Hao, Xin-Qi,Song, Mao-Ping
-
p. 403 - 411
(2016/04/19)
-
- NOVEL PRECATALYST SCAFFOLDS FOR CROSS-COUPLING REACTIONS, AND METHODS OF MAKING AND USING SAME
-
The present invention provides novel transition-metal precatalysts that are useful in preparing active coupling catalysts. In certain embodiments, the precatalysts of the invention are air-stable and moisture-stable. The present invention further provides methods of making and using the precatalysts of the invention.
- -
-
Page/Page column 60; 61
(2016/05/02)
-
- AROMATIC HETEROCYCLIC COMPOUNDS AND THEIR APPLICATION IN PHARMACEUTICALS
-
Provided herein are novel aromatic heterocyclic compounds or a stereoisomer, a geometric isomer, a tautomer, an N-oxide, a hydrate, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof, and their uses for treating Alzheimer's disease. Also provided herein are pharmaceutical compositions containing such compounds, and methods for using such compounds or pharmaceutical compositions thereof to treat Alzheimer's disease.
- -
-
Paragraph 00323
(2015/07/07)
-
- Buchwald-Hartwig Amination of (Hetero)Aryl Tosylates Using a Well-Defined N-Heterocyclic Carbene/Palladium(II) Precatalyst
-
The cross-coupling of aryl tosylates with amines and anilines was achieved by using for the first time a Pd-NHC system based on the popular Pd-PEPPSI precatalyst platform in which the anchoring imidazol-2-ylidene ligand IPr (NMe2)2 incorporates two dimethylamino groups as backbone substituents enhancing both the electronic and steric properties of the carbene. The system optimization and its application scope are disclosed.
- Zhang, Yin,Lavigne, Guy,César, Vincent
-
p. 7666 - 7673
(2015/08/18)
-
- Design of a versatile and improved precatalyst scaffold for palladium-catalyzed cross-coupling: (η3-1-tBu-indenyl)2(μ-Cl)2Pd2
-
We describe the development of (η3-1-tBu-indenyl)2(μ-Cl)2Pd2, a versatile precatalyst scaffold for Pd-catalyzed cross-coupling. Our new system is more active than commercially available (η3-cinnamyl)2(μ-Cl)2Pd2 and is compatible with a range of NHC and phosphine ligands. Precatalysts of the type (η3-1-tBu-indenyl)Pd(Cl)(L) can either be isolated through the reaction of (η3-1-tBu-indenyl)2(μ-Cl)2Pd2 with the appropriate ligand or generated in situ, which offers advantages for ligand screening. We show that the (η3-1-tBu-indenyl)2(μ-Cl)2Pd2 scaffold generates highly active systems for a number of challenging cross-coupling reactions. The reason for the improved catalytic activity of systems generated from the (η3-1-tBu-indenyl)2(μ-Cl)2Pd2 scaffold compared to (η3-cinnamyl)2(μ-Cl)2Pd2 is that inactive PdI dimers are not formed during catalysis.
- Melvin, Patrick R.,Nova, Ainara,Balcells, David,Dai, Wei,Hazari, Nilay,Hruszkewycz, Damian P.,Shah, Hemali P.,Tudge, Matthew T.
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p. 3680 - 3688
(2015/06/16)
-
- Arylation of Amines in Alkane Solvents by using Well-Defined Palladium-N-Heterocyclic Carbene Complexes
-
The use of the ITent-based series of Pd-N-heterocyclic carbenes precatalysts (Tent= Tentacular) enables the Buchwald-Hartwig amine arylation reaction in apolar alkane solvents. The use of such solvents is rare because of their poor solvation properties. Nonetheless, they could be of interest for industrial applications, as they can be disposed of in an energetically favorable manner and may potentially simplify product isolation. The excellent solubility of the precatalysts permitted the desired products to be obtained in yields ranging from 75 to 96 %, even with deactivated and functionalized coupling partners. Fueling cross-couplings: The use of ITent-based Pd precatalysts (Tent=tentacular) enables the Buchwald-Hartwig amine arylation reaction in alkane solvents. Such solvents could be of interest for industrial applications, as they can be disposed of in an energetically favorable manner and may potentially simplify product isolation. Yields ranging from 75 to 96 % are obtained, even with challenging substrates.
- Marelli, Enrico,Chartoire, Anthony,Le Duc, Gaetan,Nolan, Steven P.
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p. 4021 - 4024
(2015/12/26)
-
- "throwing away" a different ancillary ligand to enhance the catalytic activity at room temperature
-
A considerable effort in ligand design for catalysis in recent years has led to remarkable achievements in cross-coupling reactions. In this work, we show that a careful selection of the ancillary ligands that complete the catalyst/precatalyst can provide
- Guest, Daniel,Chen, Ming-Tsz,Tizzard, Graham J.,Coles, Simon J.,Turner, Michael Lewis,Navarro, Oscar
-
p. 2200 - 2203
(2014/05/20)
-
- "Throwing away" a different ancillary ligand to enhance the catalytic activity at room temperature
-
A considerable effort in ligand design for catalysis in recent years has led to remarkable achievements in cross-coupling reactions. In this work, we show that a careful selection of the ancillary ligands that complete the catalyst/precatalyst can provide an extra level of performance. Low loadings of [(IPr)PdCl2(TEA)] {IPr = 1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazole-2-ylidene, TEA = triethylamine} catalyze the Buchwald-Hartwig amination reactions of aryl chlorides at room temperature in excellent yields, without the need for an inert atmosphere to set up or perform the reactions.
- Guest, Daniel,Chen, Ming-Tsz,Tizzard, Graham J.,Coles, Simon J.,Turner, Michael Lewis,Navarro, Oscar
-
supporting information
p. 2200 - 2203
(2015/04/27)
-
- Solvent-free Buchwald-Hartwig reaction of aryl and heteroaryl halides with secondary amines
-
A highly efficient solvent-free protocol for the Buchwald-Hartwig amination of (hetero)aryl halides by secondary amines was developed. The reaction is mediated by a Pd(OAc)2/RuPhos catalytic system in air. Various (hetero)aryl halides were coupled with diaryl, alkyl-aryl, and dialkylamines in good to excellent yields (51 examples, 50-99% yield). Copyright
- Topchiy, Maxim A.,Asachenko, Andrey F.,Nechaev, Mikhail S.
-
p. 3319 - 3322
(2014/06/09)
-
- PRMT5 INHIBITORS CONTAINING A DIHYDRO- OR TETRAHYDROISOQUINOLINE AND USES THEREOF
-
Described herein are compounds of Formula (A), pharmaceutically acceptable salts thereof, and pharmaceutical compositions thereof. Compounds of the present invention are useful for inhibiting PRMT5 activity. Methods of using the compounds for treating PRMT5- mediated disorders are also described.
- -
-
Paragraph 00318
(2014/07/08)
-
- Modular synthesis of functionalisable alkoxy-tethered N-heterocyclic carbene ligands and an active catalyst for buchwald-hartwig aminations
-
Modular syntheses of functionalised, alkoxy-tethered 1,3-bis(2,4,6- trimethylphenyl)imidazolium (IMes*H+) and 1,3-bis(2,6- diisopropylphen-l)imidazolium (IPr*H+) derivatives 1,3-bis(4-alkyl- -2,4,6-trimethylphenyl)imidazolium (IXyOR*H+) and 1,3-bis(4-alkyl-oxy-2,6-diisopropylphenyl)imidazolium (IPrOR*H +) are reported. A reliable synthesis of the key starting material 4-amino-3,5-diisopropylphenol is also described. Etherification of hydroxydecorated ligand intermediates before formation of the imidazolium core and subsequent modification, or direct etherification of the versatile synthon IPrOH·HCl, allowed access to various linker types including triethoxysilyl, primary amino and norbornenyl, which are not accessible by other methods. An IPrOR-palladium(II) complex was prepared, and its catalytic activity was evaluated in challenging Buchwald- Hartwig aminations of aryl chlorides. This precatalyst displayed excellent activity and selectivity under mild reaction conditions, achieving in some cases a 10-fold improvement in TOF relative to the IPr-based version. An unexpected activity profile was observed wherein sterically demanding anilines were coupled more easily than those lacking orthosubstitution.
- Krinsky, Jamin L.,Martinez, Alberto,Godard, Cyril,Castillon, Sergio,Claver, Carmen
-
supporting information
p. 460 - 474
(2014/05/20)
-
- 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)
-
- Design and preparation of new palladium precatalysts for C-C and C-N cross-coupling reactions
-
A series of easily prepared, phosphine-ligated palladium precatalysts based on the 2-aminobiphenyl scaffold have been prepared. The role of the precatalyst-associated labile halide (or pseudohalide) in the formation and stability of the palladacycle has been examined. It was found that replacing the chloride in the previous version of the precatalyst with a mesylate leads to a new class of precatalysts with improved solution stability and that are readily prepared from a wider range of phosphine ligands. The differences between the previous version of precatalyst and that reported here are explored. In addition, the reactivity of the latter is examined in a range of C-C and C-N bond forming reactions.
- Bruno, Nicholas C.,Tudge, Matthew T.,Buchwald, Stephen L.
-
p. 916 - 920
(2013/06/05)
-
- Solvent-free aryl amination catalysed by [Pd(NHC)] complexes
-
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.
-
p. 3840 - 3843
(2013/04/23)
-
- [Pd(IPr*OMe)(acac)Cl]: Tuning the N-heterocyclic carbene in catalytic C-N bond formation
-
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.
-
supporting information
p. 330 - 339
(2013/02/25)
-
- Transition-metal-free electrophilic amination of arylboroxines
-
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
-
experimental part
p. 4230 - 4233
(2012/09/22)
-
- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
-
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
-
p. 9236 - 9239,4
(2012/12/12)
-
- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
-
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
-
p. 9236 - 9239
(2013/01/15)
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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; 50-51
(2012/07/27)
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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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- [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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- 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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- 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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- 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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- 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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- Cyclopropenylidene carbene ligands in palladium catalysed coupling reactions: Carbene ligand rotation and application to the Stille reaction
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Reaction of [Pd(PPh3)4] with 1,1-dichloro-2,3- diarylcyclopropenes gives complexes of the type cis-[PdCl2(PPh 3)(C3(Ar)2)] (Ar = Ph 5, Mes 6). Reaction of [Pd(dba)2] with 1,1-dichloro-2,3-diarylcyclopropenes in benzene gave the corresponding binuclear palladium complexes trans-[PdCl2(C 3(Ar)2)]2 (Ar = Ph 7, p-(OMe)C 6H48, p-(F)C6H49). Alternatively, when the reactions were performed in acetonitrile, the complexes trans-[PdCl2(NCMe)(C3(Ar)2)] (Ar = Ph 10, p-(OMe)C6H411 and p-(F)C6H4) 12) were isolated. Addition of phosphine ligands to the binuclear palladium complex 7 or acetonitrile adducts 11 and 12 gave complexes of the type cis-[PdCl 2(PR3)(C3(Ar)2)] (Ar = Ph, R = Cy 13, Ar = p-(OMe)C6H4, R = Ph 14, Ar = p-(F)C 6H4, R = Ph 15). Crystal structures of complexes 6·3.25CHCl3, 10, 11·H2O and 12-15 are reported. DFT calculations of complexes 10-12 indicate the barrier to rotation about the carbene-palladium bond is very low, suggesting limited double bond character in these species. Complexes 5-9 were tested for catalytic activity in C-C coupling (Mizoroki-Heck, Suzuki-Miyaura and, for the first time, Stille reactions) and C-N coupling (Buchwald-Hartwig amination) showing excellent conversion with moderate to high selectivity.
- Chotima, Ratanon,Dale, Tim,Green, Michael,Hey, Thomas W.,McMullin, Claire L.,Nunns, Adam,Guy Orpen,Shishkov, Igor V.,Wass, Duncan F.,Wingad, Richard L.
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supporting information; experimental part
p. 5316 - 5323
(2011/06/27)
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- Synthesis and X-ray structure determination of highly active Pd(II), Pd(I), and Pd(0) complexes of Di(tert -butyl)neopentylphosphine (DTBNpP) in the arylation of amines and ketones
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The air-stable complex Pd(eta;3-allyl)(DTBNpP)Cl (DTBNpP = di(tert-butyl)neopentylphosphine) serves as a highly efficient precatalyst for the arylation of amines and enolates using aryl bromides and chlorides under mild conditions with yields ranging from 74% to 98%. Amination reactions of aryl bromides were carried out using 1-2 mol % Pd(η3-allyl)(DTBNpP)Cl at 23-50 °C without the need to exclude oxygen or moisture. The C-N coupling of the aryl chlorides occurred at relatively lower temperature (80-100 °C) and catalyst loading (1 mol %) using the Pd(eta;3-allyl) (DTBNpP)Cl precatalyst than the catalyst generated in situ from DTBNpP and Pd2(dba)3 (100-140 °C, 2-5 mol % Pd). Other Pd(DTBNpP)2-based complexes, (Pd(DTBNpP)2 and Pd(DTBNpP)2Cl2) were ineffective precatalysts under identical conditions for the amination reactions. Both Pd(DTBNpP)2 and Pd(DTBNpP)2Cl2 precatalysts gave nearly quantitative conversions to the product in the α-arylation of propiophenone with p-chlorotoluene and p-bromoanisole at a substrate/catalyst loading of 100/1. At lower substrate/ca'alyst loading (1000/1), the conversions were lower but comparable to that of Pd(t-Bu3P)2. In many cases, the tri-tert-butylphosphine (TTBP) based Pd(I) dimer, [Pd(μ-Br)(TTBP)] 2, stood out to be the most reactive catalyst under identical conditions for the enolate arylation. Interestingly, the air-stable Pd(I) dimer, Pd2(DTBNpP)2(μ-Cl)(μ-allyl), was less active in comparison to [Pd(μ-Br)(TTBP)]2 and Pd(eta;3-allyl) (DTBNpP)Cl. The X-ray crystal structures of Pd(eta;3-allyl)(DTBNpP) Cl, Pd(DTBNpP)2Cl2, Pd(DTBNpP)2, and Pd 2(DTBNpP)2(μ-Cl)(μ-allyl) are reported in this paper along with initial studies on the catalyst activation of the Pd(eta;3-allyl)(DTBNpP)Cl precatalyst.
- Hill, Lensey L.,Crowell, Jason L.,Tutwiler, Strudwick L.,Massie, Nicholas L.,Hines, C. Corey,Griffin, Scott T.,Rogers, Robin D.,Shaughnessy, Kevin H.,Grasa, Gabriela A.,Johansson Seechurn, Carin C. C.,Li, Hongbo,Colacot, Thomas J.,Chou, Joe,Woltermann, Christopher J.
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supporting information; experimental part
p. 6477 - 6488
(2010/12/24)
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- 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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- 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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- 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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- Insight into the steric and electronic effects of ancillary ligands: Synthesis and structure-reactivity relationship of well-defined, air- and moisture-stable (NHC)Pd(sal)Cl complexes (sal = salicylaldimine)
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Synthesis of a series of (NHC)Pd(sal)Cl complexes, 1-5, bearing a salicylaldimine (sal) unit was described. The structure-reactivity relationship, especially the steric and electronic effects of the salicylaldimine ligands on their catalytic activities, was investigated intensively in the Buchwald-Hartwig coupling reaction. Our study demonstrated that the sterically encumbered N-aryl groups in the salicylaldimine unit give rise to an obviously negative effect in the aryl amination reaction. Additionally, incorporating a steric substituent into the ortho-position of the phenoxide oxygen atom does not appear to be beneficial to their catalytic activity. Notably, the electronic nature of N-substituted aryl groups in the salicylaldimine ligands plays a significant role in their catalytic activities. An electron-rich N-aryl group causes an obviously decreasing yield, while an electron-deficient one, such as complex 5b, leads to enhanced reactivity. The aryl amination reaction with complex 5b was also found to be remarkably tolerant to both air and moisture. Under optimized reaction conditions, a range of aryl chlorides and amines could be coupled smoothly under aerobic conditions.
- Jin, Zhong,Qiu, Ling-Ling,Li, Yan-Qing,Song, Hai-Bin,Fang, Jian-Xin
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experimental part
p. 6578 - 6586
(2011/02/16)
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- Amination and Suzuki coupling reactions catalyzed by palladium complexes coordinated by cobalt-containing monodentate phosphine ligands with bis-trifluoromethyl substituents on bridged arylethynyl: Observation of some unusual metal-containing compounds
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Two cobalt-containing bulky monodentate phosphines {[(μ-PPh2CH2PPh2)Co2(CO)4][(μ,η-(tBu)2PC{triple bond, long}CAr]} (4cm: Ar = 3-CF3C6H4; 4cmm: A
- Huang, Po-Cheng,Hong, Fung-E.
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scheme or table
p. 113 - 121
(2009/04/10)
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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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