- Single electron transfer reductive cleavage of the aryl-nitrogen bond in phenyl-substituted dimethylanilines
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By treatment with Li metal in THF at room temperature the three isomeric N,N-dimethylaminobiphenyls and N,N-dimethyl-2,6-diphenylaniline underwent 100% regioselective reductive cleavage of the aryl-N bond, affording biphenyl and meta-terphenyl, respectively, in various yields.
- Azzena,Dessanti,Melloni,Pisano
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Read Online
- A straightforward synthesis of 4,5-dihalofunctionalized imidazol-2-ylidene/imidazolyl-metal complexes from trihaloimidazolium salts/imidazoles: Structure and catalytic studies
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Backbone dihalofunctionalized imidazol-2-ylidene/imidazolyl-metal complexes (5?13) of group–10 metal ions were synthesized through a proficient and single step oxidative addition method using 2,4,5-trihaloimidazolium salts or imidazoles respectively. The donor property of 4,5-diiodofunctionalized imidazol-2-ylidene was described for the first time. The catalytic activity of palladium complexes containing imidazol-2-ylidene (6 and 7)/imidazolyl (10 and 11) groups towards Suzuki-Miyaura coupling reaction of aryl bromides was evaluated and compared with its unsubstituted counterpart. Besides, the investigation of reaction pathway in catalysis was carried out.
- Avinash, Iruthayaraj,Gupta, Vivek,Karthik, Vedhagiri,Anantharaman, Ganapathi
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Read Online
- Nickel(II) benzimidazolin-2-ylidene complexes with thioether-functionalized side chains as catalysts for Suzuki-Miyaura cross-coupling
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Four bis(benzimidazolin-2-ylidene) nickel(II) complexes featuring thioether moieties in the side chain have been synthesized by reactions of the respective benzimidazolium salts with nickel(II) acetate in molten tetrabutylammonium bromide as an ionic liqu
- Bernhammer, Jan C.,Huynh, Han Vinh
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Read Online
- Suzuki cross-coupling of hexachlorobenzene promoted by the Buchwald ligands
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The study of cross-coupling between hexachlorobenzene and phenylboronic acid comprised five Buchwald ligands, from which 2-dicyclohexylphosphino-2′-(dimethylamino)biphenyl (DavePHOS) provided the best conversion. When excess of phenylboronic acid was used, a mixture of isomeric tri-, tetra- and pentaphenyl-substituted derivatives in the ～10:70:20 ratio was obtained, along with minor amounts of hydrodechlorination products.
- Burukin, A. S.,Vasil’ev, A. A.,Zhdankina, G. M.,Zlotin, S. G.
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p. 169 - 172
(2022/02/17)
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- Buchwald ligand-assisted Suzuki cross-coupling of polychlorobenzenes
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Screening of four Buchwald ligands for the cross-coupling of isomeric di-, tri- and tetrachlorobenzenes with arylboronic acids revealed that good yields of exhaustive substitution can be best provided by 2-dicyclohexylphosphino-2′-(dimethylamino) biphenyl (DavePHOS).
- Burukin, Alexander S.,Vasil'ev, Andrei A.,Zhdankina, Galina M.,Zlotin, Sergei G.
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p. 400 - 402
(2021/06/07)
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- Tris-NHC-propagated self-supported polymer-based Pd catalysts for heterogeneous C-H functionalization
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Three-dimensionally propagated imidazolium-containing mesoporous coordination polymer and organic polymer-based platforms were successfully exploited to develop single-site heterogenized Pd-NHC catalysts for oxidative arene/heteroarene C-H functionalization reactions. The catalysts were efficient in directed arene halogenation, and nondirected arene and heteroarene arylation reactions. High catalytic activity, excellent heterogeneity and recyclability were offered by these systems making them promising candidates in the area of heterogeneous C-H functionalization, where efficient catalysts are still scarce.
- Choudhury, Joyanta,Dutta, Tapas Kumar,Mandal, Tanmoy,Mohanty, Sunit
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supporting information
p. 10182 - 10185
(2021/10/12)
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- New Nickel-Based Catalytic System with Pincer Pyrrole-Functionalized N-Heterocyclic Carbene as Ligand for Suzuki-Miyaura Cross-Coupling Reactions
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A new catalytic system with Ni(NO3)2·6H2O as the catalyst and a pincer pyrrole-functionalized N-heterocyclic carbene as the ligand was employed in the Suzuki-Miyaura cross-coupling reactions of aryl iodides with arylboronic acids. With 5 mol% catalyst, the catalytic reactions proceeded at 160 °C, giving coupling products in isolated yields of up to 94% in short reaction times (1-4 h). The system worked efficiently with aryl iodides bearing electron-donating or electron-withdrawing groups and arylboronic acids with electron-donating groups. Steric effects were observed for both aryl iodides and arylboronic acids. It is proposed that the reactions underwent a Ni(I)/Ni(III) catalytic cycle.
- Guo, Zhifo,Lei, Xiangyang
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supporting information
(2021/09/11)
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- Copper-catalyzed meta-selective arylation of phenol derivatives: An easy access to m-aryl phenols
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Achieving selective meta-functionalization of phenols is a significant challenge. Accessing such compounds generally needs elevated temperature or incorporation of complex templates. Here, we report a general approach to achieve meta-arylated phenols with a simple and common directing group. This coppercatalyzed protocol proceeds with complete meta-selectivity and tolerates a variety of functional groups in both coupling partners. Computational studies have revealed that the reaction proceeded via a Heck-like pathway.
- Maraswami, Manikantha,Hirao, Hajime,Loh, Teck-Peng
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p. 2302 - 2309
(2021/02/20)
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- PRODUCTION METHOD OF COUPLING COMPOUND
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PROBLEM TO BE SOLVED: To provide a production method of a coupling compound due to a cross-coupling reaction that uses a novel reaction substrate. SOLUTION: A production method of a coupling compound characterized by producing a compound (C) from a compound (A) and a compound (B) according to a coupling reaction represented by the following formula (1). As a reaction substrate of a cross-coupling reaction, by using a compound having a -SF5 group, which is excellent in safety and has no problem of toxicity of a byproduct, various kinds of coupling compounds may be produced at a high yield. (In the formula (1), R1 and R2 represent independently an arbitrary monovalent atomic group, Z represents a leaving group, and M represents a transition metal catalyst.) SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0069-0070
(2021/05/05)
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- Palladium (II)–Salan Complexes as Catalysts for Suzuki–Miyaura C–C Cross-Coupling in Water and Air. Effect of the Various Bridging Units within the Diamine Moieties on the Catalytic Performance
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Water-soluble salan ligands were synthesized by hydrogenation and subsequent sulfonation of salens (N,N’-bis(slicylidene)ethylenediamine and analogues) with various bridging units (linkers) connecting the nitrogen atoms. Pd (II) complexes were obtained in reactions of sulfosalans and [PdCl4]2?. Characterization of the ligands and complexes included extensive X-ray diffraction studies, too. The Pd (II) complexes proved highly active catalysts of the Suzuki–Miyaura reaction of aryl halides and arylboronic acid derivatives at 80 ?C in water and air. A comparative study of the Pd (II)–sulfosalan catalysts showed that the catalytic activity largely increased with increasing linker length and with increasing steric congestion around the N donor atoms of the ligands; the highest specific activity was 40,000 (mol substrate) (mol catalyst × h)?1. The substrate scope was explored with the use of the two most active catalysts, containing 1,4-butylene and 1,2-diphenylethylene linkers, respectively.
- Bunda, Szilvia,Joó, Ferenc,Kathó, ágnes,Udvardy, Antal,Voronova, Krisztina
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supporting information
(2020/09/18)
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- Organocatalyst in Direct C(sp2)-H Arylation of Unactivated Arenes: [1-(2-Hydroxyethyl)-piperazine]-Catalyzed Inter-/Intra-molecular C-H Bond Activation
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This article describes the identification of 1-(2-hydroxyethyl)-piperazine as a new, cost-effective, highly efficient organocatalyst, which promotes both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in the presence of potassium tert-butoxide. While the inter-molecular C-H arylation of unactivated benzenes with aryl halides (Ar-X; X = I, Br, Cl) toward biaryl syntheses underwent smoothly in the presence of only 10 mol percent organocatalyst, the intra-molecular C-H arylation catalytic system composed of 40 mol percent each of the catalyst and the additive (4-dimethylaminopyridine (DMAP)). The novel catalyst was also able to perform both inter- A nd intra-molecular direct arylations simultaneously in a single pot. The mechanistic studies confirmed the involvement of aryl radical anions and proceeded via a single-electron-transfer (SET) mechanism. The large substrate scope, high functional group tolerance, competition experiments, gram-scale synthesis, and kinetic studies further highlight the importance and versatile nature of the methodology as well as the compatibility of the new catalyst. To the best of our knowledge, this is the first report on any organocatalyst that reported detailed investigations of both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in a single representation.
- Yadav, Lalit,Tiwari, Mohit K.,Shyamlal, Bharti Rajesh Kumar,Chaudhary, Sandeep
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p. 8121 - 8141
(2020/07/16)
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- Metal-free and solvent-free synthesis of: M -terphenyls through tandem cyclocondensation of aryl methyl ketones with triethyl orthoformate
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Reported here is a novel cyclocondensation of aryl methyl ketones and triethyl orthoformate for the simple synthesis of m-terphenyls. In the presence of a catalytic amount of TfOH, alkyl- and chloro-substituted acetophenones produced a series of terphenyls through a tandem reaction which merged six steps into a one-pot procedure. Moreover, the corresponding ester products were obtained when using other substituted acetophenones as the starting materials under the same reaction conditions.
- Gan, Zongjie,Jiang, Wengao,Luo, Juan,Tang, Qiang,Xiao, Xiaoqin
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p. 12113 - 12118
(2020/04/10)
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- Preparation method of m-terphenyl compounds
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The invention provides a method for synthesizing an m-terphenyl compound by taking aryl methyl ketone and triethyl ortho-formate as raw materials. The method comprises the following steps: heating a mixture of aryl methyl ketone and triethyl ortho-formate to 50 DEG C under the protection of inert gas, adding trifluoro-methane sulfonic acid, carrying out reactions, and separating the reaction products after the reaction is finished to obtain the m-terphenyl compound. The provided synthetic method has the advantages of easily available raw materials, low cost, mild reaction conditions, simple and easily controllable operation, no need of any metal catalyst and solvent, short reaction time, good economic benefit and suitability for industrial mass production.
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Paragraph 0003
(2020/06/16)
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- Facile Synthesis of Pd Nanoparticles Incorporated into Ultrathin Crystalline g-C3N4with Enhanced Photocatalytic Performance
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Driving chemical reactions by use of sunlight is of great importance for a sustainable future. Pd-based catalysts are commonly employed in thermal catalysis for various chemical reactions such as hydrogenation and coupling reactions. However, very few reports were related to Pd for photocatalytic coupling reactions. In this work, a facile method was developed to synthesize ultra-small Pd nanoparticles anchored on ultrathin crystalline graphitic carbon nitride (g-C3N4) for photocatalysis. Monodisperse Pd nanoparticles with a diameter of about 3 nm were dispersed on ultrathin crystalline g-C3N4 uniformly. The prepared Pd/g-C3N4 catalyst could take the advantages of the unique properties of ultra-small Pd nanoparticles and ultrathin crystalline g-C3N4 and thus exhibited markedly enhanced photocatalytic performance toward Suzuki-Miyaura coupling reaction under visible light irradiation. The preparing method could also be extended to the synthesis of Ru/g-C3N4, Pt/g-C3N4, and Ag/g-C3N4.
- Cao, Changyan,Huang, Yan,Jiang, Mengying,Li, Jun,Peng, Li,Song, Weiguo,Yang, Shuliang
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p. 7526 - 7532
(2020/11/18)
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- Synthesis of Enaminone-Pd(II) Complexes and Their Application in Catalysing Aqueous Suzuki-Miyaura Cross Coupling Reaction
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A series of Pd(II)-enaminone complexes, termed Pd(eao)2, have been synthesized and characterized. The investigation on the catalytic activities of these new Pd(II)-reagents has proved that the Pd(eao)2-1 possesses excellent catalytic activity for the Suzuki- Miyaura cross coupling reactions of aryl bromides/chlorides with aryl/vinyl boronic acids in the environmentally benign media of aqueous PEG400 at low loading (5 mol‰). The superiority of this Pd(II)-reagent to those commercial Pd(II) and Pd(0) catalysts in catalyzing the reactions has been confirmed by parallel experiments. What's more, Pd(eao)2-2 has been found as a practical catalyst for the homo-coupling reactions of aryl boronic acids.
- Fu, Leiqing,Cao, Xiaoji,Wan, Jie-Ping,Liu, Yunyun
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p. 254 - 258
(2020/01/25)
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- Efficient construction of C–C bonds from aryl halides/aryl esters with arylboronic acids catalysed by palladium(II) thiourea complexes
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A new set of palladium(II) complexes comprising phenyl(thiazolyl)thiourea ligands have been successfully synthesized and characterized with the aid of analytical as well as spectral (IR, UV–visible and NMR) methods. A distorted square-planar geometry with N^S coordination mode of thiourea ligands in the new palladium complexes was corroborated by single-crystal X-ray diffraction methods. Interestingly, the palladium(II) thiourea complexes showed the highest catalytic activity with 0.1 mol% catalyst loading in Suzuki–Miyaura cross-coupling reactions utilizing a range of aryl bromides/unactivated aryl chlorides with arylboronic acids as coupling partners in aqueous–organic media. Syntheses of diaryl ketones using aryl esters and arylboronic acids as coupling partners were also achieved with low catalyst loading within 20 h. The potential of our catalyst was demonstrated by its wide substrate scope, low catalyst loadings and high isolated yield. Moreover, the influences of key parameters like solvent, base, temperature and catalyst loading were also investigated.
- Thimma Sambamoorthy, Manikandan,Rengan, Ramesh,Jan Grzegorz, Malecki
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- Palladium decorated on a new dendritic complex with nitrogen ligation grafted to graphene oxide: Fabrication, characterization, and catalytic application
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Immobilized Pd nanoparticles on a new ligand, namely, tris(pentaethylene-pentamine)triazine supported on graphene oxide (Pdnp-TPEPTA(L)-GO) was introduced as a novel and robust heterogeneous catalyst for use in C-C bond formation reaction. The Pdnp-TPEPTA(L)-GO catalyst was synthesized by complexation of Pd with TPEPTA as a ligand with high N-ligation sites that were supported on graphene oxide through 3-chloropropyltrimethoxysilane. The prepared catalyst was characterized using some microscopic and spectroscopic techniques. The TPEPTA(L)-GO substrate is a 2D heterogeneous catalyst with a high specific surface area and a large amount of N-ligation sites. The Pdnp-TPEPTA(L)-GO catalyst used in the C-C bond formation reaction between aryl or heteroaryl and phenylboronic acid derivatives was applied towards the synthesis of biaryl units in high isolated yields. Notably, a series of competing experiments were performed to establish the selectivity trends of the presented method. Also, this catalyst system was reusable at least six times without a significant decrease in its catalytic activity.
- Golestanzadeh, Mohsen,Naeimi, Hossein
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p. 27560 - 27573
(2019/09/12)
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- Pillarquinone-Based Porous Polymer for a Highly-Efficient Heterogeneous Organometallic Catalysis
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Pillar[5]quinone (PQ[5])-based porous polymer has been prepared by crosslinking and oxidating pillar[5]arene (PA[5]). Quinone was used as an unorthodox ligand to load palladium-catalyst with high loading ratio (up to 12.0 wt %). Catalyst was well dispersed on solid support in the form of Pd2+-specie. Pd-loaded PQ[5]-based heterogeneous catalyst was highly efficient for Suzuki-coupling reactions (22- to 1485-fold higher than Pd/C based on turnover frequency). It was superior compared to other existing heterogeneous catalysts for selective catalytic reaction. This heterogeneous catalyst had good thermo-stability, and could be reused and recycled.
- Lan, Shang,Yang, Xuan,Shi, Kejia,Fan, Rong,Ma, Da
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p. 2864 - 2869
(2019/06/13)
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- Visible-Light-Induced [4+2] Annulation of Thiophenes and Alkynes to Construct Benzene Rings
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The [4+2] annulation represents an elegant and versatile synthetic protocol for the construction of benzene rings. Herein, a strategy for visible-light induced [4+2] annulation of thiophenes and alkynes, to afford benzene rings, is presented. Under simple and mild reaction conditions, the ready availability and structural diversity of thiophenes and alkynes permit the facile synthesis of several substituted aromatic rings. Valuable drugs and amino acids are also well tolerated. Moreover, DFT calculations explain the high regioselectivity of the reaction.
- Song, Chunlan,Dong, Xin,Wang, Zhongjie,Liu, Kun,Chiang, Chien-Wei,Lei, Aiwen
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supporting information
p. 12206 - 12210
(2019/07/31)
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- Generation of Aryl Radicals from Aryl Halides: Rongalite-Promoted Transition-Metal-Free Arylation
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A new and practical method for the generation of aryl radicals from aryl halides is reported. Rongalite as a novel precursor of super electron donors was used to initiate a series of electron-catalyzed reactions under mild conditions. These transition-metal-free radical chain reactions enable the efficient formation of C-C, C-S, and C-P bonds through homolytic aromatic substitution or SRN1 reactions. Moreover, the synthesis of antipsychotic drug Quetiapine was performed on gram scale through the described method. This protocol demonstrated its potential as a promising arylation method in organic synthesis.
- Yu, Fazhi,Mao, Runyu,Yu, Mingcheng,Gu, Xianfeng,Wang, Yonghui
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p. 9946 - 9956
(2019/09/04)
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- N,S-chelating triazole-thioether ligand for highly efficient palladium-catalyzed Suzuki reaction
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1,2,3-Triazole-thioether compounds could serve as efficient ligands for Pd-catalyzed Suzuki reactions of various aryl iodides, bromides and chlorides. The reactions feature wide substrate scope and mild reaction conditions. Besides, shorter reaction time, lower catalyst loadings and quantitative yields with a turnover-frequency (TOF) value of up to 11,880 h?1 are other advantageous of this attractive protocol. The crystal structure analyses and computational studies revealed that the higher catalytic activity of the corresponding chelated palladium complex ascribed to the lower energy gap and the lower redox potential.
- Yan, Qiong,Zheng, Lei,Li, Miaomiao,Chen, Yunfeng
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p. 101 - 105
(2019/07/19)
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- Stereoelectronic Flexibility of Ammonium-Functionalized Triazole-Derived Carbenes: Palladation and Catalytic Activities in Water
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The postmodification approach allows convenient access to charge-tagged ammonium-functionalized bis(1,2,4-triazolin-5-ylidene)palladium(II) complexes even when the respective azolium salts are elusive. Bromo-functionalized 1,2,4-triazolium salts were first metalated to form the respective bromo-functionalized bis(NHC) complexes trans-[PdBr2(R-tazy-Br)2] (R = Ph, Cy, 1a,b). Subsequent postcoordinative nucleophilic substitutions converted the bromo into ammonium functions, leading to the water-soluble, charge-tagged complexes trans-[PdBr2(R-tazy-NEt3)2]Br2 (R = Ph, Cy, 2a,b). The catalytic activities of 2a,b in the aqueous Suzuki-Miyaura reaction were compared to those of their analogues 2c,d bearing more bulky mesityl and diisopropylphenyl substituents, and a detailed stereoelectronic profiling of the NHCs using %Vbur, HEP, and DFT calculations was conducted to rationalize their catalytic differences. Although all complexes are active, the more donating and less bulky complexes 2a,b performed significantly better than 2c,d at a very low catalyst loading of 0.001 mol %. 2a was found to be highly active for various aryl and heteroaryl bromides and some aryl chlorides. More importantly, this study discloses that NHCs with N-phenyl and N-cyclohexyl groups exhibit stereoelectronic flexibility, which could be the cause for the greater activities of their complexes.
- Nguyen, Van Ha,El Ali, Bassam M.,Huynh, Han Vinh
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p. 2358 - 2367
(2018/07/31)
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- Immobilization of an Aminobisphosphine–PdII Complex over Graphene Oxide: An Efficient and Reusable Catalyst for Suzuki–Miyaura, Ullmann Coupling and Cyanation Reactions
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The grafting of an aminobis(phosphine)–PdII complex (PNP–PdII) [PdCl2{(Ph2P)2N(CH2)3Si(OMe)3}] (2) on graphene oxide (GO) has been carried out by a condensation reaction between methoxysilane groups of 2 and hydroxyl groups of GO. The composite material was characterized by FTIR spectroscopy, solid-state 31P NMR spectroscopy, SEM, TEM, XPS and ICP-AES techniques. All these tools support the clean immobilization of compound 2 on GO. The composite material showed high catalytic activity in Suzuki–Miyaura, Ullmann coupling and cyanation reactions. The heterogeneity of the composite was confirmed by a hot filtration test. The immobilized PNP–PdII shows comparable activity to its homogeneous analogue 2. The recycling ability of the catalyst was examined for five consecutive runs, which showed little or no reduction in its catalytic efficiency.
- Sengupta, Debasish,Pandey, Madhusudan K.,Mondal, Dipanjan,Radhakrishna, Latchupatula,Balakrishna, Maravanji S.
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p. 3374 - 3383
(2018/05/08)
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- Synthesis and palladium(II) metal chemistry of thiazoline/imidazoline derived ligands: An efficient catalyst for cross-coupling reactions of arylboronic acids with acid chlorides and aryl halides
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The synthesis, reactivity, spectroscopic characterization and catalytic activities of a series of Pd(II) complexes bearing the chelating ligands 2-(4,5-dihydrothiazol-2-yl)aniline (2) and 2-(4,5-dihydro-1H-imidazol-2-yl)aniline (3) are reported. The reactions of 2 with [Pd(COD)Cl2] in 1:1 and 1:2 (ligand into metal and metal into ligand) molar ratios afforded the mononuclear complexes, PdCl2{κ2?N,S ? 2?(4,5-dihydrothiazol-2-yl)aniline} (4), Pd{κ2?N,N’?2?(4,5-dihydrothiazol-2-yl)aniline}2 (5) and Pd{κ12?N,N’?κ22?N,S ? 2?(4,5-dihydrothiazol-2-yl)aniline}2 (6), respectively, in good yields. The neutral mononuclear palladium complexes PdCl2{κ2?N,N’?(4,5-dihydro-1H-imidazol-2-yl)aniline} (7) and Pd{κ2?N,N’?2?(4,5-dihydro-1H-imidazol-2-yl)aniline}2 (8) were synthesized using [Pd(COD)Cl2] with appropriate molar ratios. The palladium complexes 4–8 were evaluated for their catalytic activities in base assisted cross coupling reactions between acid chlorides and aryl halide with boronic acids. The complex 4 was found to be an efficient catalyst for producing unsymmetrical ketones (TOF = 19.8 min?1) while complex 7 was effective for making biaryls (TOF = 19.8 min?1).
- Sudharsan, Murugesan,Suresh
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p. 598 - 608
(2018/09/18)
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- Desulfinative and denitrogenative palladium-catalyzed cross-coupling of arylsulfonyl hydrazides with aryl diazonium salts
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Palladium-catalyzed cross-coupling of arylsulfonyl hydrazides with aryl diazonium salts to provide biaryl products under relatively mild conditions is established. This reaction proceeded smoothly with tetrabutylammonium iodide and gave the corresponding
- Shang, Yonghui
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- Synthesis of Bi(hetero)aryls via Sequential Oxidation and Decarboxylation of Benzylamines in a Batch/Fully Automated Continuous Flow Process
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Catalytic dehydrogenative cross-coupling of two C–H bonds represents a green strategy in view of the atom- and step-economy. However, the challenge is to discover a new innovative bond strategy, especially for the direct coupling between Csp2–H
- Mahajan, Bhushan,Aand, Dnyaneshwar,Singh, Ajay K.
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supporting information
p. 2831 - 2835
(2018/06/21)
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- Direct Aryl-Aryl Coupling without Pre-Functionalization Enabled by Excessive Oxidation of Two-Electron Ag(I)/Ag(III) Catalyst
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Reported herein is a catalytic platform for formation of unsymmetrical biaryls by the coupling between inert Csp2?CH3 and Csp2?H via a tandem catalytic strategy. The platform utilizes traditional AgNO3 catalyst and excess amount of K2S2O8 oxidant. The excessive oxidant present converts the traditional one-electron Ag(I)/Ag(II) chemistry to two-electron Ag(I)/Ag(III) one, enabling one-pot synthesis of aryl-aryl scaffolds by using unactivated cheap commodity chemicals. (Figure presented.).
- Singh, Ajay K.,Kim, Min-Gyu,Lee, Hyune-Jea,Singh, Rakhi,Cho, Seung Hwan,Kim, Dong-Pyo
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supporting information
p. 2032 - 2042
(2018/04/11)
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- Reversible hydrogenation—dehydrogenation reactions of meta-terphenyl on catalysts with various supports
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For developing new composite systems (substrate—catalyst) for hydrogen storage, the activities of Pt and Pd catalysts on various supports were compared in reversible meta-terphenyl hydrogenation and perhydro-meta-terphenyl dehydrogenation. The microstructure of the catalysts was studied. Carbon-supported catalysts are more efficient in both reversible reactions than alumina-supported systems.
- Kalenchuk,Davshan,Bogdan,Dunaev,Kustov
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- Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions
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The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe3)3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH2PPh2)2C6H4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.
- Qi, Xinghao,Sun, Hongjian,Li, Xiaoyan,Fuhr, Olaf,Fenske, Dieter
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p. 2581 - 2588
(2018/02/28)
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- Acetylacetonato-based pincer-type nickel(ii) complexes: Synthesis and catalysis in cross-couplings of aryl chlorides with aryl Grignard reagents
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In this work, three different types of acetylacetonato-based pincer-type nickel(ii) complexes (2) were prepared. Complex 2a possessed the tridentate ONN ligand, which was constructed by the condensation reaction of acetylacetone with N,N-diethylethylenediamine. Complex 2b contained the PPh2 donor group in contrast to the NEt2 group in 2a, i.e., an ONP ligand framework. Complex 2c was composed of the NNN ligand, which was prepared by the reaction of 4-((2,4,6-trimethylphenyl)amino)pent-3-en-2-one with N,N-diethylethylenediamine. In addition to X-ray diffraction analysis, these complexes were characterized spectroscopically. Their catalytic activity for a cross-coupling reaction of aryl halides with aryl Grignard reagents was also evaluated. Among these complexes, 2b acted as an effective catalyst for the cross-coupling reaction using aryl chlorides as electrophiles. The electronic properties of these Ni(ii) complexes were investigated by cyclic voltammetry and density functional theory calculations.
- Asano, Erika,Hatayama, Yuki,Kurisu, Nobutaka,Ohtani, Atsufumi,Hashimoto, Toru,Kurihara, Youji,Ueda, Kazuyoshi,Ishihara, Shinji,Nagao, Hirotaka,Yamaguchi, Yoshitaka
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p. 8003 - 8012
(2018/06/29)
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- Stable ferrocenyl-NHC Pd(II) complexes: Evidence of C-H ?H/π interaction and M-O bonding in solution
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New air stable palladium(II)-NHC complexes where carbene ligand is substituted with a bulky ferrocenylmethyl and pyranylmethyl groups viz. PdI(Phpy){FcCH2-C3H2N2-Me} (3), PdI2{FcCH2-C3H2N2-C6H11O} (4) and PdI2{FcCH2-NHC}(L) (5–10) (NHC = C3H2N2-Me or C6H11O; L = pyridine, imidazole and thiazole) are reported. The presence of C-H?H/π interactions has been confirmed for complex 3 by NOE interaction and multinuclear NMR experiments. In addition, for this complex, a quantum chemical analysis was performed using PM3 semi-empirical calculations to find the possible conformers. The conformation with minimal energy confirms the NMR interpretation for complex 3. The M-O bond in complex 4 was ruptured by the reaction of an extra pyridine ligand to afford PdI2{FcCH2-C3H2N2-C6H11O}(py) (5) which was synthetized differently by reacting NHC ligand, Pd(OAc)2 and pyridine. Molecular structure of complex 5 was determined by X-ray diffraction. The catalytic activity of these complexes was checked in Suzuki-Miyaura reaction. Complex 5 exhibits excellent conversions and selectivities (up to 99%).
- Azpiroz, Ramón,Sharma, Pankaj,Javier Pérez-Flores,Gutierrez, René,Espinosa-Pérez, Georgina,Lara-Ochoa, Francisco
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p. 196 - 206
(2017/08/10)
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- ONE STEP DIRECT ARYLATION OF COMMODITY CHEMICALS TO SPECIALTY CHEMICALS BY TANDEM CATALYTIC PLATFORM
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The present invention relates to a continuous direct arylation process based on a tandem catalyst for synthesizing specialty chemicals. A method for synthesizing an aryl-aryl structure from a substrate selected from the group consisting of benzyl alcohol, benzyl amine and toluene which are low value added compounds is developed using a silver ion-containing tandem catalyst. The method is applied for synthesizing hexaphenyl arylene and can be applied for synthesizing high value added compounds (not only natural substances and chemical compounds but pharmaceutical and agricultural pesticide relative fields) directly from primary raw materials through the reaction.COPYRIGHT KIPO 2017
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Paragraph 0063; 0067; 0106
(2018/02/28)
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- PRODUCTION METHOD OF COUPLING COMPOUND
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PROBLEM TO BE SOLVED: To provide a production method of a coupling compound due to a cross-coupling reaction that uses a novel reaction substrate. SOLUTION: A production method of a coupling compound characterized by producing a compound (C) from a compound (A) and a compound (B) according to a coupling reaction represented by the following formula (1). As a reaction substrate of a cross-coupling reaction, by using a compound having a -SF5 group, which is excellent in safety and has no problem of toxicity of a byproduct, various kinds of coupling compounds may be produced at a high yield. (In the formula (1), R1 and R2 represent independently an arbitrary monovalent atomic group, Z represents a leaving group, and M represents a transition metal catalyst.) SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0069; 0070
(2018/03/23)
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- Insight into Copper Catalysis: In Situ Formed Nano Cu2O in Suzuki-Miyaura Cross-Coupling of Aryl/Indolyl Boronates
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A ligand-free copper catalyzed Suzuki-Miyaura coupling of 3,5-diiodopyridine with aryl and indole boronates has been explored in good to excellent yields. In situ generation of nano-Cu2O from CuCl2 under the reaction conditions has been discovered for the first time. The generality of the reaction was further demonstrated by the arylation of 5-iodopyrimidine, iodopyridines, iodobenzenes, and diiodobenzenes and resulted in good to moderate yields. Moreover, bisindole alkaloid Scalaridine A has been successfully synthesized in 60% overall yield.
- Ranjani, Ganapathy,Nagarajan, Rajagopal
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p. 3974 - 3977
(2017/08/14)
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- Arylation of hydrocarbons enabled by organosilicon reagents and weakly coordinating anions
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Over the past 80 years, phenyl cation intermediates have been implicated in a variety of C-H arylation reactions. Although these examples have inspired several theoretical and mechanistic studies, aryl cation equivalents have received limited attention in organic methodology. Their high-energy, promiscuous reactivity profiles have hampered applications in selective intermolecular processes. We report a reaction design that overcomes these challenges. Specifically, we found that b-silicon-stabilized aryl cation equivalents, generated via silylium-mediated fluoride activation, undergo insertion into sp3 and sp2 C-H bonds. This reaction manifold provides a framework for the catalytic arylation of hydrocarbons, including simple alkanes such as methane. This process uses low loadings of Earth-abundant initiators (1 to 5 mole percent) and occurs under mild conditions (30° to 100°C).
- Shao, Brian,Bagdasarian, Alex L.,Popov, Stasik,Nelson, Hosea M.
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- Synthesis and catalytic activity of nickel(II) complexes containing NCN pincer ligands
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In this study, nickel(II) complexes [LmeNi(II)Cl]+(BPh4)?, [LmeNi(II)Cl]+(PF6)? and [Let2Ni(II)]+(BPh4)?2 were synthesised and characterized in the solution and solid states. Ligands Lme (C11H12N6) and Let (C13H17N6) featured a central carbene donor linked to pendant pyrazoles via either methylene or ethylene linkers. The catalytic activity of all three complexes was tested in the Kumada cross coupling reaction between phenylmagnesium bromide and aromatic halogen substituted substrates. [LmeNi(II)Cl]+(BPh4)?was found to be the most active catalyst.
- Nair, Ashwin G.,McBurney, Roy T.,Gatus, Mark R.D.,Walker, D.Barney,Bhadbhade, Mohan,Messerle, Barbara A.
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- Palladium-catalyzed synthesis of diarylbenzenes from coupling reactions between equal amount of diiodoarenes and arylboronic acids
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We reported a highly effective Pd-catalytic system for the synthesis of diarylbenzenes through Suzuki-type reaction between equal amount of diiodoarenes and arylboronic acids. This preferential oxidative addition resulted in such high selectivity.
- Mao, Jincheng,Li, Ran,He, Yue,Yang, Xiaojiang,Wang, Dingli,Zhang, Yang
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p. 663 - 669
(2016/07/26)
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- Efficient Catalyst for Both Suzuki and Heck Cross-Coupling Reactions: Synthesis and Catalytic Behaviour of Geometry- Constrained Iminopyridylpalladium Chlorides
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A series of geometry-constrained iminopyridyl-palladium chlorides were synthesized and characterized. These phosphine-free palladium complexes were explored for their catalytic activities in both Suzuki and Heck cross-coupling reactions, achieving turnover numbers as high as 106towards various aryl bromides, even those containing various functionalities. In addition, the influence of substituents with steric and electronic factors was reflected by the differences observed in their activities. (Figure presented.).
- Tang, Yujie,Zeng, Yanning,Hu, Qingxia,Huang, Fang,Jin, Liqun,Mo, Weimin,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan,Sun, Wen-Hua
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p. 2642 - 2651
(2016/08/31)
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- Highly efficient palladium(II) hydrazone based catalysts for the Suzuki coupling reaction in aqueous medium
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Synthesis of a new family of air stable palladium(ii)benzhydrazone complexes of the general formula [PdCl(PPh3)(L)] (where HL = thiophene aldehyde benzhydrazones) incorporating PPh3 and chloride as co-ligands has been described through a single and convenient step with good yields. All the new complexes have been fully characterized by means of elemental analysis, IR, UV-vis, and NMR spectral methods. The molecular structures of three of the complexes were determined by single crystal X-ray crystallography, which confirm the coordination mode of benzhydrazone and reveal the presence of a distorted square planar geometry around the Pd ion. The complexes 1-5 (0.05 mol%) have been found to be a highly active catalytic system in the mono and double Suzuki-Miyaura cross coupling reaction of deactivated aryl and heteroaryl bromides with different types of aryl boronic acids in neat water and the maximum yield was up to >99%. Notably, these catalysts work well with ultra-low loading of the catalysts and show high turnover numbers in a short time towards different substrates. Moreover, the catalysts could be simply recovered and reused five times without significant loss of efficiency.
- Muthumari, Subramanian,Ramesh, Rengan
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p. 52101 - 52112
(2016/06/13)
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- Synthesis, structure and catalytic applications of octahedral nickel(II) benzoylhydrazone complex: Suzuki-Miyaura cross-coupling reaction of aryl bromides with arylboronic acid
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A simple route for the synthesis of a new octahedral nickel(II) complex (1) containing 4-chloro-benzoic acid pyridin-2-ylmethylene-hydrazide ligand (HL, where H represents the dissociable proton) has been described. The characterization of the complex having the formula [Ni(μ3-O,N,N-L)2] has been established by elemental analysis, ESI-MS, spectral methods and single crystal X-ray crystallography. Further, the new complex was found to act as an active homogeneous catalyst for the Suzuki-Miyaura reaction of substituted aryl bromides (mono and dibromides) with various arylboronic acids having different electronic effects under optimized conditions of solvent, base and catalyst loading. The biphenyl and triphenyl derivatives were obtained in moderate to excellent isolated yields.
- Suganthy, Pandimuni Kalpaga,Prabhu, Rupesh Narayana,Sridevi, Venugopal Shanmugham
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p. 127 - 132
(2016/06/01)
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- Kinetic and thermodynamic parameters of hydrogen release during the heterogeneous catalytic dehydrogenation of cis- and trans-isomers of perhydro-m-terphenyl
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Comparative studies on the temperature dependence of the dehydrogenation of cis- and trans-isomers of perhydro-m-terphenyl are performed in a flow catalytic reactor. Rate constants and equilibrium constants of all elementary acts of this reaction are calculated on basis of experimental data using the KINET 0.8 program for the mathematical modeling of the kinetics of complex reactions. The resulting data indicate that perhydro-m-terphenyl cis- and trans-isomers structural differences have no appreciable effect on dehydrogenation.
- Kalenchuk,Bogorodskii,Bogdan
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p. 1921 - 1924
(2016/09/23)
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- Pd-catalyzed Suzuki–Miyaura cross-coupling of [Ph2SR][OTf] with arylboronic acids
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The Pd-catalyzed Suzuki–Miyaura cross-coupling of alkyl- and fluoroalkyl(diphenyl)sulfonium triflates with arylboronic acids was compared. The fluorine substitution on the alkyl groups of [Ph2SR][OTf] had a big influence on the reaction. Perfluoroalkyl(diphenyl)sulfonium triflates (2b–d) were unsuccessful participants in the Pd-catalyzed phenylation of arylboronic acid under the standard conditions because of the strong electronegativity of the long-chain perfluoroalkyl groups, which underwent S[sbnd]Rfnbond cleavage instead. Polyfluoroalkyl(diphenyl)sulfonium triflates (2f–h) reacted with arylboronic acid to afford the phenylation product in very low yields due to the tendency of deprotonation and β-F elimination of the sulfonium salts. Eventually, (2,2,2-trifluoroethyl)diphenylsulfonium triflate (2e), methyl- or ethyl(diphenyl)sulfonium triflate (2i or 2j), and triphenylsulfonium triflate (2m) were found to be more effective reagents than other tested phenylsulfounium salts for Pd-catalyzed phenylation, which provided much higher yields of the desired products under mild conditions.
- Wang, Xiao-Yan,Song, Hai-Xia,Wang, Shi-Meng,Yang, Jing,Qin, Hua-Li,Jiang, Xin,Zhang, Cheng-Pan
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p. 7606 - 7612
(2016/11/11)
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- Gold(i)-catalyzed dehydrogenative cycloisomerization of 1,5-enynes
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The gold(i)-catalyzed dehydrogenative cycloisomerization of cyclopropane-tethered 1,5-enynes proceeded smoothly to give multisubstituted benzene derivatives in good to excellent yields. Synthetically important benzocyclobutenes can be produced in high yields in the presence of a gold(i) catalyst and DDQ. Furthermore, this reaction also works very well for non-cyclopropane tethered 1,5-enynes.
- Chen, Gen-Qiang,Fang, Wei,Wei, Yin,Tang, Xiang-Ying,Shi, Min
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supporting information
p. 10799 - 10802
(2016/09/07)
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- Infrared irradiation or microwave assisted cross-coupling reactions using sulfur-containing ferrocenyl-palladacycles
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The synthesis of four new sulfur-containing palladacycles 3a-d [FcC(S)OEtPdClZR3, where: 3a, ZR3: PPh3; 3b, ZR3: P(o-Tol)3; 3c, ZR3: PMe3; 3d, ZR3: SbPh3] from ferrocenyl thionoester 1 [FcC(S)OEt] in good yields is reported. The catalytic applications of these cyclopalladated complexes in Heck and Suzuki cross-coupling reactions were also evaluated, in combination with infrared or microwave as energy sources. The coupled products of these reactions were obtained in good to excellent yields, short reaction times and low catalyst loading.
- Balam-Villarreal,Sandoval-Chávez,Ortega-Jiménez,Toscano,Carreón-Castro,López-Cortés,Ortega-Alfaro
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- TfOH-Catalyzed Reaction of Bispropargyl Alcohols with 1,3-Dicarbonyl Compounds
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A transition-metal-free efficient method for the preparation of 1,2,3-trisubstituted benzenes from bispropargyl alcohols and 1,3-dicarbonyl compounds has been developed. The reaction of bispropargyl alcohol with 1,3-dicarbonyl compound proceeds through [3,3]-rearrangement, 6π-electrocyclization, and unexpected Csp3-Csp2 regioselective σ-bond cleavage processes.
- Teng, Qinghu,Mo, Shikun,Pan, Jiankun,Wu, Na,Wang, Hengshan,Pan, Yingming
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p. 455 - 461
(2016/01/28)
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- Synthesis and Reactivity of N-Heterocyclic PSiP Pincer Iron and Cobalt Complexes and Catalytic Application of Cobalt Hydride in Kumada Coupling Reactions
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The new N-heterocyclic σ-silyl pincer ligand HSiMe(NCH2PPh2)2C6H4 (1) was designed. A series of tridentate silyl pincer Fe and Co complexes were prepared. Most of them were formed by chelate-assisted Si-H activation. The typical iron hydrido complex FeH(PMe3)2(SiMe(NCH2PPh2)2C6H4) (2) was obtained by Si-H activation of compound 1 with Fe(PMe3)4. The combination of compound 1 with CoMe(PMe3)4 afforded the Co(I) complex Co(PMe3)2(SiMe(NCH2PPh2)2C6H4) (3). The Co(III) complex CoHCl(PMe3)(SiMe(NCH2PPh2)2C6H4) (5) was generated by the reaction of complex 1 with CoCl(PMe3)3 or the combination of complex 3 with HCl. However, when complex 3 was treated with MeI, the Co(II) complex CoI(PMe3)(SiMe(NCH2PPh2)2C6H4) (4), rather than the Co(III) complex, was isolated. The catalytic performance of complex 5 for Kumada coupling reactions was explored. With a catalyst loading of 5 mol %, complex 5 displayed efficient catalytic activity for Kumada cross-coupling reactions of aryl chlorides and aryl bromides with Grignard reagents. This catalytic reaction mechanism is proposed and partially experimentally verified.
- Xiong, Zichang,Li, Xiaoyan,Zhang, Shumiao,Shi, Yaomin,Sun, Hongjian
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p. 357 - 363
(2016/02/19)
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- Pd-catalyzed desulfitative and denitrogenative Suzuki-type reaction of arylsulfonyl hydrazides
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A palladium-catalyzed desulfitative-denitrogenative coupling of arylsulfonyl hydrazides and arylboronic acids with the assistance of catalytic ligands is described. The reaction showed very good selectivity and tolerated a wide range of functionalities without the aid of expensive copper- or silver-based stoichiometric co-oxidants. We have successfully applied this new cross-coupling reaction to the synthesis of terphenyls and OTBN.
- Zhong, Shuangling,Sun, Chenggang,Dou, Sen,Liu, Wencong
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p. 27029 - 27033
(2015/03/30)
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- Ligand-controlled chemoselectivity in potassium tert-amylate-promoted direct C-H arylation of unactivated benzene with aryl halides
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Direct C-H arylation of unactivated benzene with aryl halides under various simple ligands (EDA, DMEDA, ethylene glycol, etc.) in the presence of potassium tert-amylate (t-AmOK) base at mild temperature (80 °C) have been developed. This transition-metal-free radical cross-coupling offers an efficient way to synthesize various biaryls in good yields through base-promoted homolytic aromatic substitution. And mechanistic investigations have provided insight into the chemoselectivity of couplings between haloiodobenzenes and benzene and showed that phenanthroline and its derivatives not only initiate these radical reactions like most of other ligands (EDA, DMEDA, ethylene glycol, etc.), but also participate in the electron transfer process of biaryl radical anion intermediates.
- Liu, Wei,Xu, Lige
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p. 4974 - 4981
(2015/06/25)
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- Copper-Catalyzed Coupling of Triaryl- and Trialkylindium Reagents with Aryl Iodides and Bromides through Consecutive Transmetalations
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An efficient copper(I)-catalyzed coupling of triaryl and trialkylindium reagents with aryl iodides and bromides is reported. The reaction proceeds at low catalyst loadings (2 mol %) and generally only requires 0.33 equivalents of the triorganoindium reagent with respect to the aryl halide as all three organic nucleophilic moieties of the reagent are transferred to the products through consecutive transmetalations. The reaction tolerates a variety of functional groups and sterically hindered substrates. Furthermore, preliminary mechanistic studies that entailed the synthesis and characterization of potential reaction intermediates offered a glimpse of the elementary steps that constitute the catalytic cycle.
- Thapa, Surendra,Gurung, Santosh K.,Dickie, Diane A.,Giri, Ramesh
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supporting information
p. 11620 - 11624
(2016/02/19)
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- Rhodium-catalyzed cross-coupling of aryl carbamates with arylboron reagents
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A new method has been developed for the rhodium-catalyzed cross-coupling of aryl carbamates with organoboron reagents. The use of an NHC ligand bearing a 2-adamantyl group, i.e., I(2-Ad), is essential to the success of the reaction. The reaction involves the rhodium-mediated activation of the relatively inert C(aryl)-O bond of aryl carbamates.
- Nakamura, Keisuke,Yasui, Kosuke,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 4484 - 4489
(2015/03/30)
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- Using ceramic membranes for the separation of hydrogen produced by dehydrogenation of perhydro-m-terphenyl
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The efficiency of a variety of ceramic membranes for the purification of hydrogen obtained by dehydrogenation of perhydro-m-terphenyl in a catalytic flow reactor from vapors of initial hydrocarbons and dehydrogenation products is investigated.
- Kalenchuk,Bogdan,Kustov
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- PtI2-catalyzed cyclization of 3-acyloxy-1,5-enynes with the elimination of HOAc and a benzyl shift: Synthesis of unsymmetrical m-terphenyls
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A novel cyclization of 3-acyloxy-1,5-enynes is developed in the presence of PtI2 for the synthesis of substituted unsymmetrical m-terphenyls in good to excellent yields. Two unique steps are involved in this transformation, which includes the elimination of HOAc and benzyl group migration. DFT calculations indicated that the rate-determining step is the migration of the benzylic carbocation to form a zwitterionic intermediate followed by the elimination of HOAc. The subsequent cyclopropanation of the zwitterionic intermediate is the regioselectivity-determining step.
- Huang, Kaimeng,Ke, Xiaona,Wang, Hongkai,Wang, Junying,Zhou, Chenchen,Xu, Xiufang,Liu, Lingyan,Li, Jing
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p. 4486 - 4493
(2015/04/14)
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