- Inverse-electron-demand Diels-Alder reactions of 4-aryl-2-pyrones with electron-rich dienophiles
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The Diels-Alder reaction of 4-aryl-pyrones with electron-rich dienophiles afforded substituted biaryl derivatives in most cases. At the minimal temperatures necessary for a measurable conversion of the starting pyrones, the bicyclic lactones, the primary products of the condensation, underwent cycloreversion by extruding carbon dioxide and then aromatised through further eliminations. In the case of the more active 4-aryl-6-chloro-pyrone, a formal substitution was observed instead of the expected cycloaddition with an active dienophile, while in its reaction with a Schiff-base the primary product of the cycloaddition was trapped through the formation of a new tetrahydropyridine derivative. (C) 2000 Elsevier Science Ltd.
- Balazs,Kadas,Toke
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Read Online
- Nickel-Catalyzed Direct Cross-Coupling of Aryl Sulfonium Salt with Aryl Bromide
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The direct cross-couplings of aryl sulfonium salts with aryl halides could be achieved by using nickel as a reaction catalyst. The reactions proceeded efficiently via C-S bond activation in the presence of magnesium turnings and lithium chloride in THF at ambient temperature to afford the corresponding biaryls in moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions employing preprepared organometallic reagents.
- Ma, Na-Na,Ren, Jing-Ao,Liu, Xiang,Chu, Xue-Qiang,Rao, Weidong,Shen, Zhi-Liang
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p. 1953 - 1957
(2022/03/27)
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- Organocatalytic synthesis of (Het)biaryl scaffoldsviaphotoinduced intra/intermolecular C(sp2)-H arylation by 2-pyridone derivatives
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A uniqueN,O-bidentate ligand 6-oxo-1,6-dihydro-pyridone-2-carboxylic acid dimethylamide (L1) catalyzed direct C(sp2)-H (intra/intermolecular) arylation of unactivated arenes has been developed to expedite access to (Het)biaryl scaffolds under UV-irradiation at room temperature. The protocol tolerated diverse functional groups and substitution patterns, affording the target products in moderate to excellent yields. Mechanistic investigations were also carried out to better understand the reaction pathway. Furthermore, the synthetic applicability of this unified approach has been showcasedviathe construction of biologically relevant 4-quinolone, tricyclic lactam and sultam derivatives.
- Das, Tapas Kumar,Kundu, Mrinalkanti,Mondal, Biswajit,Ghosh, Prasanjit,Das, Sajal
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p. 208 - 218
(2021/12/29)
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- Designing biaryl phosphacyclic ligands: their characterization and evaluation in palladium-catalyzed Suzuki-Miyaura reactions of aryl bromides and chlorides
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Efficient palladium catalyst systems based on the combination of bench stable biaryl phosphacycles and Pd(OAc)2 are described for Suzuki-Miyaura cross-coupling reactions of aryl bromides and chlorides. Notably, the electronically and sterically diametric biaryl phosphacycles allowed facile coupling of sterically hindered and heterocyclic substrates.
- Holzapfel, Cedric W.,Lamola, Jairus L.,Maumela, Munaka Christopher,Moshapo, Paseka T.
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- Cobalt-Catalyzed Coupling of Aryl Chlorides with Aryl Boron Esters Activated by Alkoxides
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The cobalt-catalyzed Suzuki biaryl cross-coupling of aryl chloride substrates with aryl boron reagents, activated with more commonly used bases, remained a significant unmet challenge in the race to replace platinum group metal catalysts with Earth-abundant metal alternatives. We now show that this highly desirable process can be realized using alkoxide bases, provided the right counterion is employed, strict stoichiometric control of the base is maintained with respect to the aryl boron reagent, and the correct boron ester is selected. Potassium tert-butoxide works well, but any excess of the base first inhibits and then poisons the catalyst. Lithium tert-butoxide performs very poorly, while even catalytic amounts of lithium additives also poison the catalyst. Meanwhile, a neopentane diol-based boron ester is required for best performance. As well as delivering this sought-after transformation, we have undertaken detailed mechanistic and computational investigations to probe the possible mechanism of the reaction and help explain the unexpected experimental observations.
- Tailor, Sanita B.,Manzotti, Mattia,Smith, Gavin J.,Davis, Sean A.,Bedford, Robin B.
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p. 3856 - 3866
(2021/04/07)
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- Electrochemical Synthesis of Biaryls via Oxidative Intramolecular Coupling of Tetra(hetero)arylborates
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We report herein versatile, transition metal-free and additive-free (hetero)aryl-aryl coupling reactions promoted by the oxidative electrocoupling of unsymmetrical tetra(hetero)arylborates (TABs) prepared from ligand-exchange reactions on potassium trifluoroarylborates. Exploiting the power of electrochemical oxidations, this method complements the existing organoboron toolbox. We demonstrate the broad scope, scalability, and robustness of this unconventional catalyst-free transformation, leading to functionalized biaryls and ultimately furnishing drug-like small molecules, as well as late stage derivatization of natural compounds. In addition, the observed selectivity of the oxidative coupling reaction is related to the electronic structure of the TABs through quantum-chemical calculations and experimental investigations.
- Music, Arif,Baumann, Andreas N.,Spie?, Philipp,Plantefol, Allan,Jagau, Thomas C.,Didier, Dorian
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p. 4341 - 4348
(2020/03/04)
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- Suzuki-Miyaura Cross-Coupling of Sulfoxides
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The utilization of diphenyl sulfoxides as versatile electrophilic coupling partners for the Suzuki-Miyaura reaction via C-S bond cleavage was successfully developed under palladium-N-heterocyclic carbene catalysis. The reactions showed good functional group compatibility, proceeded well under mild conditions, and provided biaryls in yields of up to 96%. A wide range of useful functional groups, such as fluoro, chloro, ether, hydroxyl, amide, cyano, keto, trimethylsilyl (TMS), and ester were tolerated under the reaction conditions; however, the use of phenylboronic anhydride and arylboronic acid pinacol esters generally would lead low yields. Good regioselectivity for the electron-poor phenyl group was achieved when unsymmetrical diphenyl sulfoxides were used. The protocol is applicable at the gram scale even with half the amount of catalyst. Density functional theory calculations were performed to investigate the reaction mechanism, indicating that the reaction occurred through oxidative addition, transmetalation, and reductive elimination to provide the final coupling product.
- Abduhulam, Hayrul,Cao, Changsheng,Chen, Qianwei,Dang, Yanfeng,Li, Chengxi,Shi, Yanhui,Wu, Shufeng,Yan, Shuqin
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p. 8168 - 8176
(2020/09/18)
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- Decarbonylative Suzuki-Miyaura Cross-Coupling of Aroyl Chlorides
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Herein, we report a catalyst system for Pd-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of aroyl chlorides with boronic acids to furnish biaryls. This strategy is suitable for a broad range of common aroyl chlorides and boronic acids. The synthetic utility is highlighted in the direct late-stage functionalization of pharmaceuticals and natural products capitalizing on the presence of carboxylic acid moiety. Extensive mechanistic and DFT studies provide key insight into the reaction mechanism and high decarbonylative cross-coupling selectivity.
- Zhou, Tongliang,Xie, Pei-Pei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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supporting information
p. 6434 - 6440
(2020/09/02)
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- Palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides by carbon-nitrogen bond activation
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Palladium-catalyzed Suzuki-Miyaura cross-coupling or aryl halides is widely employed in the synthesis of many important molecules in synthetic chemistry, including pharmaceuticals, polymers and functional materials. Herein, we disclose the first palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides for the synthesis of biaryls through the selective activation of the N-C(O) bond of amides. This new method relies on the precise sequence engineering of the catalytic cycle, wherein decarbonylation occurs prior to the transmetallation step. The reaction is compatible with a wide range of boronic acids and amides, providing valuable biaryls in high yields (>60 examples). DFT studies support a mechanism involving oxidative addition, decarbonylation and transmetallation and provide insight into high N-C(O) bond activation selectivity. Most crucially, the reaction establishes the use of palladium catalysis in the biaryl Suzuki-Miyaura cross-coupling of the amide bond and should enable the design of a wide variety of cross-coupling methods in which palladium rivals the traditional biaryl synthesis from aryl halides and pseudohalides.
- Zhou, Tongliang,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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p. 9865 - 9871
(2019/11/11)
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- Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes
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Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes are described. This redox neutral strategy offers an efficient approach to diverse biaryls, vinyl arenes and arylacetylenes. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the in situ formation of Ph3PAuIR (R = aryl, vinyl and alkynyl) species which is crucial for the activation of aryldiazonium salts.
- Akram, Manjur O.,Shinde, Popat S.,Chintawar, Chetan C.,Patil, Nitin T.
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supporting information
p. 2865 - 2869
(2018/05/03)
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- Denitrogenative Pd/Cu-catalyzed Suzuki-type Cross-coupling of Aryltrifluoroborates with Arylhydrazine Hydrochlorides in Water under Room Temperature
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A water-soluble palladium-catalyzed Suzuki-type cross-coupling of aryltrifluoroborates with arylhydrazide hydrochlorides was efficiently developed under mild and environmentally benign conditions, in water without any ligand. The newly developed Pd/Cu co-catalyzed denitrogenative reaction gave a range of structurally diverse substituted biaryls with good to excellent yields, in which the byproduct was nitrogen.
- Wang, Guofang,Meng, Mengting,Deng, Liping,Cheng, Kai,Qi, Chenze
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- Palladium nanoparticles stabilized by phosphine ligand for aqueous phase room temperature suzuki-Miyaura coupling
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Water soluble phosphine ligand triphenylphosphine-3,3′,3″-trisulfonic acid trisodium salt (TPPTS) was used as the stabilizer as well as the activator to the palladium nanoparticles, which showed a high catalytic performance for aqueous phase Suzuki-Miyaura coupling reaction at room temperature.
- Ge, Jiyuan,Jiang, Jian,Yuan, Chenhuan,Zhang, Chaozhi,Liu, Minghua
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supporting information
p. 1142 - 1145
(2017/03/02)
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- SOLID-SUPPORTED PALLADIUM (II) COMPLEX AS A HETEROGENEOUS CATALYST FOR CROSS COUPLING REACTIONS AND METHODS THEREOF
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A solid-supported catalyst ligand which chelates palladium (II) species to form a complex that functions as a heterogeneous catalyst that is stable and can be recycled without significantly losing any catalytic activity in a variety of chemical transformations, a method for producing the solid-supported catalyst ligand and a method for catalyzing a palladium cross-coupling reaction, such as the Suzuki-Miyaura, Mizoroki-Heck, and Sonagashira reactions.
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Paragraph 0134-0137
(2017/10/10)
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- Transition-Metal-Free Cross-Coupling of Aryl and Heteroaryl Thiols with Arylzinc Reagents
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Cross-coupling of (hetero)arylthiols with arylzinc reagents via C-S cleavage was performed under transition-metal-free conditions. The reaction displays a wide scope of substrates and high functional-group tolerance. Electron-rich and -deficient (hetero)arylthiols and arylzinc reagents can be employed in this transformation. Mg2+ and Li+ ions were demonstrated to facilitate the reaction.
- Yang, Bo,Wang, Zhong-Xia
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p. 6220 - 6223
(2017/11/24)
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- Nickel-Catalyzed Deamidative Step-Down Reduction of Amides to Aromatic Hydrocarbons
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To date, cleavage of the C-N bond in aromatic amides has been achieved in molecules with a distorted constitutional framework around the nitrogen atom. In this report, a nickel-catalyzed reduction of planar amides to the corresponding lower hydrocarbon homologue has been reported. This involves a one-pot reductive cleavage of the C-N bond followed by a tandem C-CO bond break in the presence of a hydride source. Substrate scope circumscribes deamidation examples which proceed via oxidative addition of nickel in the amide bonds of nontwisted amides. Mechanistic studies involving isolation and characterization of involved intermediates via different spectroscopic techniques reveal a deeper introspection into the plausible catalytic cycle for the methodology.
- Dey, Aniruddha,Sasmal, Sheuli,Seth, Kapileswar,Lahiri, Goutam Kumar,Maiti, Debabrata
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p. 433 - 437
(2017/06/05)
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- A General Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl and Heteroaryl Chlorides
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A general palladium-catalyzed Hiyama cross-coupling reaction of aryl and heteroaryl chlorides with aryl and heteroaryl trialkoxysilanes by a Pd(OAc)2/L2 catalytic system is presented. A newly developed water addition protocol can dramatically improve the product yields. The conjugation of the Pd/L2 system and the water addition protocol can efficiently catalyze a broad range of electron-rich, -neutral, -deficient, and sterically hindered aryl chlorides and heteroaryl chlorides with excellent yields within three hours and the catalyst loading can be down to 0.05 mol % Pd for the first time. Hiyama coupling of heteroaryl chlorides with heteroaryl silanes is also reported for the first time. The reaction can be easily scaled up 200 times (100 mmol) without any degasification and purification of reactants; this facilitates the practical application in routine synthesis.
- Yuen, On Ying,So, Chau Ming,Man, Ho Wing,Kwong, Fuk Yee
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supporting information
p. 6471 - 6476
(2016/05/09)
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- Nickel/N-Heterocyclic Carbene-Catalyzed Suzuki-Miyaura Type Cross-Coupling of Aryl Carbamates
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The utility of N-heterocyclic carbene ligands in nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl esters and carbamates is investigated. Imidazol-2-ylidene bearing 2-adamantyl groups at its nitrogen atoms generates the most active nickel species among the ligands examined, allowing cross-coupling of a range of aryl carbamates and pivalates. Unlike the previously reported system using tricyclohexylphosphine, this protocol is suitable for the cross-coupling using arylboronic esters in addition to arylboronic acids.
- Ohtsuki, Akimichi,Yanagisawa, Kousuke,Furukawa, Takayuki,Tobisu, Mamoru,Chatani, Naoto
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p. 9409 - 9414
(2016/10/17)
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- Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates
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The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts - multimetallic catalysis - can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts - (bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium - enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this reaction will simplify the synthesis of pharmaceuticals, many of which are currently made with pre-formed organometallic reagents, and lead to the discovery of new multimetallic reactions.
- Ackerman, Laura K. G.,Lovell, Matthew M.,Weix, Daniel J.
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p. 454 - 457
(2015/09/08)
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- Nickel- and Palladium-Catalyzed Coupling of Aryl Fluorosulfonates with Aryl Boronic Acids Enabled by Sulfuryl Fluoride
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Herein are reported examples of the nickel- and palladium-catalyzed cross-coupling of aryl fluorosulfonates and aryl boronic acids. These reactions occur in good to excellent yields under mild conditions with excellent functional group compatibility employing either Pd(OAc)2 and inexpensive PPh3 or the inexpensive and readily available NiCl2(PCy3)2. Importantly, the in situ conversion of phenol derivatives to the corresponding aryl fluorosulfonate by reaction with sulfuryl fluoride and a base and subsequent cross-coupling to form biaryls in a single pot are described. The combination of inexpensive sulfuryl fluoride and efficient catalysts reported in these methodologies will enable economical Suzuki coupling of phenols in pharmaceutical and agrochemical processes.
- Hanley, Patrick S.,Krasovskiy, Arkady L.,Ober, Matthias S.,Whiteker, Gregory T.,Kruper, William J.
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p. 5041 - 5046
(2015/09/15)
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- METHOD FOR COUPLING A FIRST AROMATIC COMPOUND TO A SECOND AROMATIC COMPOUND
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In one aspect, there is provided a method of coupling a first aromatic compound having a fluorosulfonate substituent to a second aromatic compound having a boron-containing substituent. In another aspect, there is provided a method of coupling a first aromatic compound having a hydroxyl substituent to a second aromatic compound having a boron-containing substituent in a one-pot reaction.
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Paragraph 00142-00144
(2015/11/24)
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- A green approach for the decoration of Pd nanoparticles on graphene nanosheets: An in situ process for the reduction of C-C double bonds and a reusable catalyst for the Suzuki cross-coupling reaction
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A new strategy for in situ synthesis of palladium nanoparticles (Pd NPs) decorated on reduced graphene oxide (rGO) nanosheets with controlled size and shape is reported. This strategy was designed as three processes in one pot, namely, (a) reduction of graphene oxide, (b) formation of Pd NPs on the rGO nanosheets and (c) simultaneous reduction of olefin. In this synthesis process, a hydrogen atmosphere was used to develop the Pd NPs-rGO nanocatalyst, which is reusable and easily separable. The influence of the size and morphology of the Pd-rGO-H2 catalyst on the catalytic activity in the Suzuki cross-coupling reaction was investigated by comparing with other catalysts, Pd-rGO-As and Pd-rGO-Gl, and they were synthesized by different reducing agents, ascorbic acid and glucose, respectively. The catalysts were characterized by electron microscopy (HRTEM, SEM), FT-IR, XRD and XPS. The Pd-rGO-H2 catalyst was found to possess excellent catalytic activity and recyclability in the Suzuki cross-coupling reaction under mild reaction conditions.
- Hussain, Najrul,Borah, Ashwini,Darabdhara, Gitashree,Gogoi, Pranjal,Azhagan, Vedi Kuyil,Shelke, Manjusha V.,Das, Manash R.
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p. 6631 - 6641
(2015/08/06)
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- Bisamino(diphosphonite) with dangling olefin functionalities: Synthesis, metal chemistry and catalytic utility of Rhi and Pdii complexes in hydroformylation and Suzuki-Miyaura reactions
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Bisamino(diphosphonite), p-C6H4{N{P(OC 6H4C3H5-o)2} 2}2 (1), was prepared by reacting p-C6H 4{N(PCl2)2}2 with four equivalents of o-allylphenol in 85% yield. Compound 1 on treatment with [M(CO) 4(HNC5H10)2] (M = Mo or W) gave cis-[{M(CO)4}2{p-C6H4{N(P(OC 6H4C3H5-o)2) 2}2}] (2, M = Mo; 3, M = W). The reaction of 1 with [Fe(η5-C5H5)(CO)2]2 yielded the complex [{Fe(η5-C5H5)(μ-CO)} 2{p-C6H4{N(P(OC6H4C 3H5-o)2)2}2}] (4). Treatment of 1 with Fe(CO)5 furnished a mononuclear complex, [{Fe(CO)3}2{p-C6H4{N{P(OC 6H4C3H5-o)2} 2}2}] (5). The ruthenium(ii) complex, [{(η 6-p-cymene)Ru(μ-Cl)3RuCl}2{p-C 6H4{N(P(OC6H4C3H 5-o)2)2}2}] (6), was obtained on treatment of ligand 1 with [(η6-p-cymene)Ru(Cl)2] 2. The reaction between 1 and [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) in dichloromethane resulted in the formation of a dinuclear complex [{RhCl}2{p-C6H4{N(P(OC 6H4C3H5-o)2) 2}2}] (7), in which the allyl double bond of one of the phenoxy groups coordinates to the metal center. When ligand 1 was reacted with two equivalents of [Pd(COD)Cl2], a dinuclear complex [{PdCl 2}2{p-C6H4{N(P(OC6H 4C3H5-o)2)2} 2}] (8) was obtained. With copper(i) halides, ligand 1 afforded tetranuclear complexes, [{(Cu(μ-X)(NCCH3))2} 2{p-C6H4{N(P(OC6H4C 3H5-o)2)2}2}] (9, X = Cl; 10, X = Br; 11, X = I). Reaction of 1 with four equivalents of [AuCl(SMe 2)] produced a tetranuclear complex, [(AuCl)4{p-C 6H4{N{P(OC6H4C3H 5-o)2}2}2}] (12). Complex 8 shows excellent catalytic activity in the Suzuki-Miyaura cross-coupling reaction under microwave conditions and complex 7 catalyzes hydroformylation of styrenes with good TONs. The Royal Society of Chemistry 2014.
- Naik, Susmita,Kumaravel, Maruthai,Mague, Joel T.,Balakrishna, Maravanji S.
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p. 1082 - 1095
(2014/01/06)
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- Application of bisphosphomide-palladium(II) pincer complex in Suzuki-Miyaura cross-coupling reaction under microwave irradiation
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The bisphosphomide-based pincer complex [PdBr{2,6-{ Ph2PC(O)} 2(C6H3)}] (2) has shown very high catalytic activity in Suzuki-Miyaura cross coupling reaction under microwave irradiation for a variety of aryl bromides and aryl boronic acids. The complex showed the same efficiency for gram scale reactions.
- Kumaravel, Maruthai,Kumar, Pawan,Balakrishna, Maravanji S
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p. 711 - 716
(2014/07/07)
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- Tandem C-H activation/arylation catalyzed by low-valent iron complexes with bisiminopyridine ligands
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Tandem C-H activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox-active non-innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first-row transition metals have been shown to involve substrate-based aryl radicals, whereas our catalytic system likely involves ligand-centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner-sphere C-H activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble-metal-like behavior could be sustained by the redox-active non-innocent bisiminopyridine ligands. A radical choice! A low-valent iron complex with non-innocent bisiminopyridine ligands performs C-H activation/arylation of unactivated aryl compounds (see figure). The reaction likely involves ligand-based radicals, whereas previously reported iron-based systems imply substrate-based radicals.
- Salanouve, Elise,Bouzemame, Ghania,Blanchard, Sebastien,Derat, Etienne,Desage-El Murr, Marine,Fensterbank, Louis
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supporting information
p. 4754 - 4761
(2014/05/06)
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- Palladium-catalyzed Suzuki cross-couplings of N′-mesyl arylhydrazines via C-N bond cleavage
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An efficient palladium-catalyzed Suzuki cross-coupling reaction of N′-mesyl arylhydrazine with aryl boronic acid is described, which affords the corresponding biaryl compounds in high yields. This transformation proceeds through C-N bond cleavage under mi
- Zhou, He-Ping,Liu, Jin-Biao,Yuan, Jian-Jun,Peng, Yi-Yuan
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p. 25576 - 25579
(2014/07/07)
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- Pd/C-catalyzed ligand-free Hiyama cross-coupling reaction of Aryl halides under aqueous conditions
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A mild and efficient ligand-free Hiyama cross-coupling reaction using Pd/C as a catalyst under aqueous conditions has been developed. A wide variety of aryl bromides undergo the cross-coupling with aryl siloxanes in excellent yields without the use of any additives. The operational simplicity and the mild reaction conditions add to the value of this method as a practical alternative to the Hiyama cross-coupling of aryl and heteroaryl halides.
- Mittapelly, Nagaraju,Mukkanti, Khagga,Reguri, Buchi Reddy
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p. 1015 - 1018
(2014/06/09)
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- Palladium-catalyzed Suzuki cross-coupling of arylhydrazines via C-N bond cleavage
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The first example of Pd-catalyzed Suzuki cross-coupling of readily available arylhydrazines with arylboronic acids via C-N bond cleavage was developed under air, affording various biaryl compounds with broad substrate applicability and moderate to good yields. Moreover, the rigorous exclusion of air/moisture is not required in these transformations. Thus, the protocol represents a simple and efficient procedure to access biaryl compounds.
- Peng, Zhimin,Hu, Gaobo,Qiao, Hongwei,Xu, Pengxiang,Gao, Yuxing,Zhao, Yufen
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p. 2733 - 2738
(2014/04/17)
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- Fibrous nano-silica (KCC-1)-supported palladium catalyst: Suzuki coupling reactions under sustainable conditions
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Noble amines recycled: Fibrous high-surface-area nano-silica functionalized with aminopropyl groups and loaded with well-dispersed Pd nanoparticles is evaluated for the Suzuki coupling of aromatic halides. It is active for the reaction of a range of aryl bromides and iodides as well as chlorides with aryl boronic acids in good to excellent yields. The catalyst can be recovered and reused for a number of cycles with negligible loss in activity. Copyright
- Fihri, Aziz,Cha, Dongkyu,Bouhrara, Mohamed,Almana, Noor,Polshettiwar, Vivek
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scheme or table
p. 85 - 89
(2012/06/29)
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- An efficient palladium-benzimidazolyl phosphine complex for the Suzuki-Miyaura coupling of aryl mesylates: Facile ligand synthesis and metal complex characterization
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A new class of easily accessible hemilabile benzimidazolyl phosphine ligands has been developed. The ligand skeleton is prepared from commercially available and inexpensive o-phenylenediamine and 2-bromobenzoic acid. With catalyst loading down to 0.5 mol% palladium, excellent catalytic activity towards the Suzuki-Miyaura coupling of aryl mesylates is still observed. This represents the lowest catalyst loading achieved so far for this reaction in general. X-Ray crystallography shows that new ligand L2 is coordinated with Pd in a κ2-P,N fashion.
- Chung, Kin Ho,So, Chau Ming,Wong, Shun Man,Luk, Chi Him,Zhou, Zhongyuan,Lau, Chak Po,Kwong, Fuk Yee
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supporting information; experimental part
p. 1967 - 1969
(2012/03/10)
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- Neutral palladium(II) complexes with P,N Schiff-base ligands: Synthesis, characterization and application as Suzuki-Miyaura coupling catalysts
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Palladium(II) complexes of the general formulae [PdCl2(PN)] and [Pd(Me)Cl(PN)] were obtained from bidentate ligands bearing phosphine and imine donor groups. The complexes were shown to be highly active catalysts for the Suzuki-Miyaura cross-coupling reaction. The complexes are tolerant of a wide variety of reaction conditions such as solvent, choice of base as well as substituents on both arylboronic acids and aryl halides.
- Mahamo, Tebello,Mogorosi, Mokgolela M.,Moss, John R.,Mapolie, Selwyn F.,Chris Slootweg,Lammertsma, Koop,Smith, Gregory S.
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experimental part
p. 34 - 42
(2012/03/26)
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- Nickel-catalyzed cross-coupling of aryl phosphates with arylboronic acids
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The Suzuki-Miyaura cross-coupling of aryl phosphates using Ni(PCy 3)2Cl2 as an inexpensive, bench-stable catalyst is described. Broad substrate scope and high efficiency are demonstrated by the syntheses of more than 40 biaryls and by constructing complex organic molecules. The poor reactivity of aryl phosphates relative to aryl halides is successfully employed to construct polyarenes by selective cross-coupling using Pd and Ni catalysts.
- Chen, Hu,Huang, Zhongbin,Hu, Xiaoming,Tang, Guo,Xu, Pengxiang,Zhao, Yufen,Cheng, Chien-Hong
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experimental part
p. 2338 - 2344
(2011/05/30)
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- Cobalt-catalyzed direct arylation of unactivated arenes with aryl halides
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Inexpensive and simple: The direct arylation of unactivated arenes with aryl halides has been carried out with [Co(acac)3] as the catalyst and LiHMDS as the base. The corresponding biaryl compounds have been prepared in good to excellent yields and at a relatively low reaction temperature (see scheme; acac=acetylacetonate, LiHMDS=lithium bis(trimethylsilyl)amide). An intramolecular direct arylation has also been achieved under the same conditions.
- Liu, Wei,Cao, Hao,Xin, Jie,Jin, Liqun,Lei, Aiwen
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supporting information; experimental part
p. 3588 - 3592
(2011/05/04)
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- Nickel-catalysed cross-coupling reaction of aryl(trialkyl)silanes with aryl chlorides and tosylates
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Using highly stable, readily accessible, and recyclable 2-(2-hydroxyprop-2-yl)cyclohexyl-substituted arylsilanes activated by a mild carbonate base, nickel-catalysed silicon-based aryl-aryl cross-coupling reaction proceeds for the first time with inexpensive aryl chlorides and tosylates in a highly chemoselective manner.
- Tang, Shi,Takeda, Masahide,Nakao, Yoshiaki,Hiyama, Tamejiro
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supporting information; experimental part
p. 307 - 309
(2011/02/24)
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- Suzuki-Miyaura cross-coupling of aryl carbamates and sulfamates: Experimental and computational studies
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The first Suzuki-Miyaura cross-coupling reactions of the synthetically versatile aryl O-carbamate and O-sulfamate groups are described. The transformations utilize the inexpensive, bench-stable catalyst NiCl 2(PCy3)2 to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups are tolerated, in addition to those that possess ortho substituents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative addition with carbamates or sulfamates occurs via a five-centered transition state, resulting in the exclusive cleavage of the aryl C-O bond. Water is found to stabilize the Ni-carbamate catalyst resting state, which thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.
- Quasdorf, Kyle W.,Antoft-Finch, Aurora,Liu, Peng,Silberstein, Amanda L.,Komaromi, Anna,Blackburn, Tom,Ramgren, Stephen D.,Houk,Snieckus, Victor,Garg, Neil K.
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scheme or table
p. 6352 - 6363
(2011/06/19)
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- Advantageous use oftBu2P-N=P(iBuNCH 2CH2)3N in the hiyama coupling of aryl bromides and chlorides
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(Chemical Equation Presentation) An efficient catalytic route to biaryls by employing (generally) only 0.25 mol % of Pd(OAc)2 and 0.5 mol % of 1 in the Hiyama coupling reaction is reported. High yields for electron-rich, -neutral, and -deficient aryl chlorides are obtained. A variety of phenylsiloxanes undergo coupling with aryl bromides and chlorides with low Pd(OAc)2/1 loadings.
- Raders, Steven M.,Kingston, Jesudoss V.,Verkade, John G.
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supporting information; experimental part
p. 1744 - 1747
(2010/05/18)
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- Iron-catalyzed direct arylation through an aryl radical transfer pathway
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(Figure Presented) A general and efficient iron-catalyzed direct arylation of benzene and hetereoaryl derivatives using a cost-effective and environmentally benign catalyst is described. The reaction is performed under neat conditions and can proceed at room temperature.
- Vallee, Frederic,Mousseau, James J.,Charette, Andre B.
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supporting information; experimental part
p. 1514 - 1516
(2010/04/04)
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- Synthesis of biaryls and oligoarenes using aryl[2-(hydroxymethyl)phenyl] dimethylsilanes
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Through intramolecular activation, highly stable aryl[2-(hydroxymethyl) phenyl]dimethylsilanes can selectively transfer their aryl groups to effect a cross-coupling reaction with various aryl bromides and chlorides in the presence of a weak non-fluoride base and a palladium/copper catalyst. This reaction tolerates a wide range of functional groups, producing the corresponding functionalized biaryls in high yields with excellent chemoselectivity. Newly disclosed reaction conditions allow the recovery of a cyclic silyl ether in modest-to-good yields and reuse for the synthesis of the arylsilanes. The introduction of two isopropyl groups on the silicon center instead of methyl groups improves the stability and allows quantitative recovery of the silicon residue. Finally, aryl halides having an O-protected [2- (hydroxymethyl)phenyl] dimethylsilyl group cross-couple with the arylsilane reagents to give silyl-functionalized biaryls. Upon deprotection, the biaryls further react with the silylated electrophiles. The iterative cross-couplingdeprotection sequences allow rapid assembly of silylated oligoarenes. Syntheses of di- and trisilyloligoarenes are also achieved by use of orthogonal O-protecting groups.
- Chen, Jinshui,Tanaka, Masaaki,Sahoo, Akhila K.,Takeda, Masahide,Yada, Akira,Nakao, Yoshiaki,Hiyama, Tamejiro
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experimental part
p. 554 - 569
(2010/07/02)
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- N,N-diethyl O-carbamate: Directed metalation group and orthogonal Suzuki-Miyaura cross-coupling partner
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(Chemical Equation Presented) The first Suzuki-Miyaura cross-coupling of an aryl O-carbamate, a versatile and powerful directed metalation group (DMG) in directed ortho metalation (DoM) chemistry, is described using the inexpensive, bench-stable catalyst NiCl2(PCy3)2. Broad synthetic scope and good efficiency are demonstrated for aryl and heteroaryl O-carbamates. The role of water and hydrolysis equilibrium between free boronic acid and boroxine was established to be a crucial parameter for this transformation. When combined with DoM and traditional Pd-catalyzed Suzuki-Miyaura strategies, the methodology offers concise routes to uniquely substituted molecules, avoiding the need for protection/deprotection of the phenol and the use of strongly nucleophilic cross-coupling partners.
- Antoft-Finch, Aurora,Blackburn, Tom,Snieckus, Victor
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supporting information; experimental part
p. 17750 - 17752
(2010/03/25)
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- Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction
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Pd2+-exchanged graphite oxide and chemically derived graphenes therefrom were employed as supports for Pd nanoparticles. The influence of catalyst preparation, carbon functionalization, and catalyst morphology on the catalytic activity in the Suzuki-Miyaura coupling reactions was investigated. The catalysts were characterized by means of spectroscopy (FT-IR, solid-state 13C NMR, AAS, XPS), X-ray scattering (WAXS), surface area analysis (BET, methylene blue adsorption), and electron microscopy (TEM, ESEM). In contrast to the conventional Pd/C catalyst, graphite oxide and graphene-based catalysts gave much higher activities with turnover frequencies exceeding 39 000 h-1, accompanied by very low palladium leaching (1 ppm).
- Scheuermann, Gil M.,Steurer, Peter,Muelhaupt, Rolf,Rumi, Luigi,Bannwarth, Willi
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supporting information; experimental part
p. 8262 - 8270
(2009/11/30)
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- Palladium-indolylphosphine-catalyzed hiyama cross-coupling of aryl mesylates
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(Chemical Equation Presented) Aryl mesylates are found to be applicable as electrophiles in organosilicon-mediated coupling reactions. The catalyst system comprising 2 mol % of Pd(OAc)2 and CM-phos supporting ligand is highly effective in catalyzing Hiyama cross-coupling of various aryl and heteroaryl mesylates. Interesting acid additive effects show that the presence of 0.25-0.50 equiv of acetic acid efficiently suppresses the mesylate decomposition and generally promotes the coupling product yields.
- So, Chau Ming,Lee, Hang Wai,Lau, Chak Po,Kwong, Fuk Yee
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supporting information; experimental part
p. 317 - 320
(2009/07/04)
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- Silicon-Based Cross-Coupling Reagent and Production Method of Organic Compound Using the Same
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In one embodiment of the present invention, a silicon-based cross-coupling reagent is disclosed which is a highly stable tetraorganosilicon compound allowing for a cross-coupling reaction under mild reaction conditions without using fluoride ions, transition metal promoter, or strong bases, and the residue of the silicon reagent can be recovered and reused. The silicon-based cross-coupling reagent is a silicon compound in which an o-hydroxymethylphenyl group is connected to a silicon atom for intramolecular activation.
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Page/Page column 21; 23-24
(2009/04/24)
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- Catalytic activities of a bis(carbene)-derived nickel(II)-pincer complex in Kumada-Tamao-Corriu and Suzuki-Miyaura coupling reactions for the synthesis of biaryl compounds
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The catalytic activities of a pincer type bis(imidazolin-2-ylidene) nickel(II) complex were evaluated. The complex was found to be an effective catalyst in the Kumada-Tamao-Corriu and Suzu-M-Miyaura coupling reactions of a broad range of aryl-X (X = Br, Cl and F) compounds, providing a variety of biaryl compounds, generally in good yield. Georg Thieme Verlag Stuttgart.
- Inamoto, Kiyofumi,Kuroda, Jun-Ichi,Sakamoto, Takao,Hiroya, Kou
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p. 2853 - 2861
(2008/03/13)
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- Suzuki-type cross-coupling reaction of pentavalent triarylantimony diacetates with arylboronic acids without a base
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Novel base-free Suzuki-type cross-coupling reaction by the use of triarylantimony diacetates and arylboronic acids in the presence of Pd(PPh3)4 catalyst led to the formation of biaryl derivatives in moderate to excellent yields. The reaction is applicable to a variety of arylboronic acids bearing base-sensitive functional groups.
- Yasuike, Shuji,Qin, Weiwei,Sugawara, Yoshiyuki,Kurita, Jyoji
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p. 721 - 724
(2007/10/03)
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- Cross-coupling of triallyl(aryl)silanes with aryl bromides and chlorides: An alternative convenient biaryl synthesis
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Cross-coupling of a diverse range of aryl bromides with triallyl(aryl)silanes is effective in the presence of PdCl2/PCy 3 and tetrabutylammonium fluoride (TBAF) in DMSO-H2O to give various biaryls in good yields. It is worthwhile to note that the all-carbon-substituted arylsilanes, stable towards moisture, acid, and base and easily accessible, serve as a highly practical alternative to their aryl(halo)silane counterparts. A catalyst system consisting of [η3-C3H5)PdCl]2 and 2-[2,4,6-(i-Pr)3C6Ha]-C6H4PCy 2 and use of TBAF· 3 H2O in THF-H2O are effective especially for the cross-coupling with aryl chlorides. Both of the catalyst systems tolerate a broad spectrum of common functional groups. The high efficiency of reactions is presumably due to the ready cleavage of the allyl groups upon treatment with TBAF·3 H2O and an appropriate amount of water. Diallyl(diphenyl)silane also cross-couples with various aryl bromides and chlorides in good yields, whereas allyl(triphenyl)silane gives the cross-coupled products in only moderate yields. Through sequential cross-coupling of bromochlorobenzenes with different arylsilanes, a range of unsymmetrical terphenyls are accessible in good overall yields.
- Sahoo, Akhila K.,Oda, Takuro,Nakao, Yoshiaki,Hiyama, Tamejiro
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p. 1715 - 1727
(2007/10/03)
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- Highly active palladium catalysts supported by bulky proazaphosphatrane ligands for stille cross-coupling: Coupling of aryl and vinyl chlorides, room temperature coupling of aryl bromides, coupling of aryl triflates, and synthesis of sterically hindered biaryls
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A family of proazaphosphatrane ligands [P(RNCH2CH 2)2N(R′NCH2CH2): R = R′ = i-Bu, 1; R = Bz, R′ = 1-Bu, 3; R = R′ = Bz, 4] for palladium-catalyzed Stille reactions of aryl chlorides is described. Catalysts derived from ligands 1 and 4 efficiently catalyze the coupling of electronically diverse aryl chlorides with an array of organotin reagents. The catalyst system based on the ligand 3 is active for the synthesis of sterically hindered biaryls (di-, tri-, and tetra-ortho substituted). The use of ligand 4 allows room-temperature coupling of aryl bromides and it also permits aryl inflates and vinyl chlorides to participate in Stille coupling.
- Su, Weiping,Urgaonkar, Sameer,McLaughlin, Patrick A.,Verkade, John G.
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p. 16433 - 16439
(2007/10/03)
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- Triallyl(aryl)silanes serve as a convenient agent for silicon-based cross-coupling reaction of aryl halides
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Triallyl(aryl)silanes, stable and easily accessible arylsilanes, were found to react with aryl bromides in the presence of a palladium catalyst (PdCl2-PCy3) and tetrabutylammonium fluoride (TBAF) in good yields. The scope of the reaction is broad, and a wide variety of functional groups are tolerant. Allyl groups on Si are readily cleaved upon treatment with TBAF to form fluorosilanes, silanepolyols, siloxanes and/or their mixed forms, which might be responsible for high efficiency of the reaction.
- Nakao, Yoshiaki,Oda, Takuro,Sahoo, K. Akhila,Hiyama, Tamejiro
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p. 570 - 573
(2007/10/03)
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- Reinvestigation of the noncatalyzed coupling of aryllithium with haloarene: A novel aromatic nucleophilic substitution pathway
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Noncatalyzed coupling reactions of aryllithiums and haloarenes proceed not only through the well-known aryne route but also, in some cases, through a novel addition-elimination pathway. Indeed, ortho-chloro- and ortho-bromomethoxyarenes lead selectively to the corresponding ortho-biaryls through a chelation-driven aromatic nucleophilic substitution pathway. Contrary to common belief, such noncatalyzed coupling reactions often proceed with high regioselectivity and high yield. These results underline the potency of such simple reactions and open up a straightforward access to a wide range of biaryl structures; this also appears particularly useful for large-scale and biaryl building-block syntheses, as only cheap and readily available substrates are involved.
- Becht, Jean-Michel,Gissot, Arnaud,Wagner, Alain,Mioskowski, Charles
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p. 3209 - 3215
(2007/10/03)
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- Palladium-catalyzed Suzuki-Miyaura reaction using aminophosphine as ligand
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Suzuki-Miyaura cross-coupling reaction has been achieved under the catalysis of Pd(OAc)2 in the presence of readily accessible and easily tunable aminophosphine ligands with high efficiency under mild reaction condition.
- Cheng, Jiang,Wang, Feng,Xu, Jian-Hua,Pan, Yi,Zhang, Zhaoguo
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p. 7095 - 7098
(2007/10/03)
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- Application of the fluorous biphase concept to palladium-catalyzed Suzuki couplings
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Suzuki C - C couplings were performed in high yields in a fluorous biphase system applying the four differently perfluoro-tagged Pd complexes 2a-d. All four complexes showed similar catalytic activities in the coupling of electron-rich or electron-deficient bromoarenes 3a-e and arylboronic acids 4a-c. Furthermore, we were able to show that all four Pd complexes could be recycled six times without significant decrease in coupling yield. In one example, we were able to reduce the amount of the four catalysts from 1.5 mol-% to 0.1 mol-% in the first runs, but with considerable loss of catalyst activity in repetitive cycles.
- Schneider, Siegfried,Bannwarth, Willi
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p. 735 - 742
(2007/10/03)
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