- C(sp2)-C(sp2) cross coupling reaction catalyzed by a water-stable palladium complex supported onto nanomagnetite particles
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A water-stable palladium complex supported onto nanomagnetite particles was prepared and characterized. The nanocatalyst showed excellent reusability and activity in aqueous phase processes including the C(sp2)-C(sp2) cross coupling reactions. The advantages of the protocol are its generality, high yields, short reaction time, a cleaner reaction profile, and simplicity.
- Azadbakht, Tahereh,Zolfigol, Mohammad Ali,Azadbakht, Reza,Khakyzadeh, Vahid,Perrin, David M.
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Read Online
- An improved Suzuki-Miyaura cross-coupling reaction for the synthesis of fluorine-substituted 3-biaryl-1-ferrocenyl-2-propen-1-one
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We studied the Pd(0)-catalyzed Suzuki-Miyaura cross-coupling reaction and obtained an improved procedure with shorter reaction times and higher conversions. We investigated two methods stepwise addition of reagents and addition of all the reagents at the
- Song, Qing-Bao,Lin, Ru-Xiang,Teng, Ming-Yu,Zhang, Jie,Ma, Chun-An
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- The Anionic Pathway in the Nickel-Catalysed Cross-Coupling of Aryl Ethers
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The Ni-catalysed cross-coupling of aryl ethers is a powerful method to forge new C?C and C?heteroatom bonds. However, the inert C(sp2)?O bond means that a canonical mechanism that relies on the oxidative addition of the aryl ether to a Ni0 centre is thermodynamically and kinetically unfavourable, which suggests that alternative mechanisms may be involved. Here, we provide spectroscopic and structural insights into the anionic pathway, which relies on the formation of electron-rich hetero-bimetallic nickelates by adding organometallic nucleophiles to a Ni0 centre. Assessing the rich co-complexation chemistry between Ni(COD)2 and PhLi has led to the structures and solution-state chemistry of a diverse family of catalytically competent lithium nickelates being unveiled. In addition, we demonstrate dramatic solvent and donor effects, which suggest that the cooperative activation of the aryl ether substrate by Ni0-ate complexes plays a key role in the catalytic cycle.
- Borys, Andryj M.,Hevia, Eva
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supporting information
p. 24659 - 24667
(2021/10/20)
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- Impact of Solvent and Their Contaminants on Pd/C Catalyzed Suzuki-Miyaura Cross-Coupling Reactions
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The aim of this work was to understand if solvent contaminants can interfere in Suzuki’s cross-coupling reactions and if it can explain the lack of robustness in industrial processes. For this purpose, several parameters were tested on the industrial model reaction between 2-bromonaphthalene and phenylboronic acid catalyzed by Pd/C. Best results were obtained using THF as solvent. Traces of the precursors of the used solvents, such as 2,3-dihydrofurane or maleic anhydride (100–300 ppm related to the solvent) strongly poisoned the reaction, decreasing the conversion significantly. This means that to ensure robust production, solvent quality must be analyzed at the ppm level. Fortunately, addition of triphenylphosphine can circumvent the catalyst poisoning.
- de Lambert de Boisjan, Alexandre,Allemann, Christophe,Fadini, Luca
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- Arylketones as Aryl Donors in Palladium-Catalyzed Suzuki-Miyaura Couplings
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Herein, we report the arylation, alkylation, and alkenylation of aryl ketones via a palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. The use of the pyridine-oxazoline ligand is the key to the cleavage of the unstrained C-C bond. The late-stage arylation of aryl ketones derived from drugs and natural products demonstrated the synthetic utility of this protocol.
- Wang, Zhen-Yu,Ma, Biao,Xu, Hui,Wang, Xing,Zhang, Xu,Dai, Hui-Xiong
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supporting information
p. 8291 - 8295
(2021/11/13)
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- METHOD FOR SYNTHESIZING BORONATE ESTER COMPOUND, SODIUM SALT OF BORONATE ESTER COMPOUND, AND METHOD FOR SYNTHESIZING THE SAME
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An object is to establish a technology with which a boronate ester compound can be easily and efficiently synthesized at a low cost with a small number of steps without the need for a complex chemical method and reagents that need to be carefully handled. A further object is to establish a sodium salt of a boronate ester compound that is a novel compound and a technology for synthesizing the sodium salt of a boronate ester compound. Provided are a sodium salt of a boronate ester compound and a method for synthesizing a boronate ester compound or a sodium salt of a boronate ester compound that includes reacting, in a reaction solvent, an organic chloride with a dispersion product obtained by dispersing sodium in a dispersion solvent to obtain an organic sodium compound, and reacting the obtained organic sodium compound with a borate ester compound to obtain a boronate ester compound or a sodium salt of a boronate ester compound.
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Paragraph 0124
(2021/03/13)
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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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- METHOD FOR SYNTHESIZING ORGANIC MAGNESIUM COMPOUND, METHOD FOR SYNTHESIZING ORGANIC BORONIC ACID COMPOUND, AND COUPLING METHOD
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An object is to establish a technology with which an organic magnesium compound can be easily and efficiently synthesized at a low cost with few steps that do not involve a complex chemical method. A method for synthesizing an organic magnesium compound includes, in a reaction solvent, reacting an organic halide represented by General Formula I (Ra—Xa) with a dispersion product obtained by dispersing sodium in a dispersion solvent to obtain an organic sodium compound represented by General Formula II (Ra—Na), and reacting the obtained organic sodium compound with a magnesium halide represented by General Formula III (Mg—(Xb)2) to obtain an organic magnesium compound represented by General Formula IV (Ra—Mg—Xb).
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Paragraph 0017; 0088-0091
(2021/03/13)
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- A photocatalytic ensemble HP-T?Au-Fe3O4: Synergistic and balanced operation in Kumada and Heck coupling reactions
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A supramolecular catalytic ensemble HP-T?Au-Fe3O4 supported by highly branched assemblies of hexaphenylbenzene (HPB) derivatives has been developed. The as-prepared HP-T?Au-Fe3O4 nanohybrid material serves as an efficient catalytic system to prepare biaryl derivatives through the Kumada cross-coupling reaction using aryl chlorides as one of the coupling partners under mild reaction conditions (visible light irradiation, aqueous media, aerial conditions, short reaction time). Through the cooperative effect of Au NPs and Fe3O4 NPs, dual activation of aryl chlorides for the generation of aryl radical intermediates is achieved. On the other hand, oligomeric assemblies contributed significantly to the enhancement of the reaction rate and yield of the product by facilitating the reductive elimination step. Different mechanistic studies confirm the involvement of Au NPs, Fe3O4 NPs and oligomeric assemblies in the synergistic and balanced operation of HP-T?Au-Fe3O4 nanohybrid materials in the efficient completion of the catalytic cycle of the Kumada coupling reaction. Being magnetic, the catalytic ensemble could be recycled for up to five catalytic cycles. The as-prepared supramolecular photocatalytic ensemble also works efficiently in Heck coupling reactions involving aryl chlorides and aryl iodides as the coupling partner.
- Bhalla, Vandana,Kaur, Harpreet,Kumar, Manoj
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supporting information
p. 8036 - 8045
(2020/11/30)
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- Synthesis of Biaryls via Decarbonylative Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Aryl Anhydrides
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Transition metal-catalyzed cross-couplings have been widely employed in the synthesis of many important molecules in synthetic chemistry for the construction of diverse C-C bonds. Conventional cross-coupling reactions require active electrophilic coupling partners, such as organohalides or sulfonates, which are not environmentally friendly enough. Herein, we disclose the first nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl anhydrides and arylboronic acids for the synthesis of biaryls in a decarbonylation manner. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents in this process.
- Zhou, Jing-Ya,Liu, Rui-Qing,Wang, Cheng-Yi,Zhu, Yong-Ming
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p. 14149 - 14157
(2020/11/13)
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- Transition-Metal-Free Oxidative Cross-Coupling of Tetraarylborates to Biaryls Using Organic Oxidants
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Readily prepared tetraarylborates undergo selective (cross)-coupling through oxidation with Bobbitt's salt to give symmetric and unsymmetric biaryls. The organic oxoammonium salt can be used either as a stoichiometric oxidant or as a catalyst in combination with in situ generated NO2 and molecular oxygen as the terminal oxidant. For selected cases, oxidative coupling is also possible with NO2/O2 without any additional nitroxide-based cocatalyst. Transition-metal-free catalytic oxidative ligand cross-coupling of tetraarylborates is unprecedented and the introduced method provides access to various biaryl and heterobiaryl systems.
- Gerleve, Carolin,Studer, Armido
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supporting information
p. 15468 - 15473
(2020/05/06)
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- para-Selective arylation and alkenylation of monosubstituted arenes using thianthreneS-oxide as a transient mediator
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Using thianthreneS-oxide (TTSO) as a transient mediator,para-arylation and alkenylation of mono-substituted arenes have been demonstratedviaapara-selective thianthrenation/Pd-catalyzed thio-Suzuki-Miyaura coupling sequence under mild conditions. This reaction features a broad substrate scope, and functional group and heterocycle tolerance. The versatility of this approach was further demonstrated by late-stage functionalization of complex bioactive scaffolds, and direct synthesis of some pharmaceuticals, including Tetriprofen, Ibuprofen, Bifonazole, and LJ570.
- Chen, Xiao-Yue,Nie, Xiao-Xue,Wu, Yichen,Wang, Peng
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p. 5058 - 5061
(2020/05/18)
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- Preparation method of para-substituted aryl compound
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The invention discloses a preparation method of a para-substituted aryl compound shown as a formula (I) which is described in the specfication. The preparation method is characterized by comprising the following step of: subjecting an aryl sulfonium salt shown as a formula (II) which is described in the specfication and boride to a coupling reaction in a solvent in an inert atmosphere under the action of alkali and a palladium catalyst to obtain the para-substituted aryl compound. According to the method, mono-substituted aromatic hydrocarbon is taken as a substrate, the aryl sulfonium salt isconstructed in situ, and the palladium catalyst catalyzes the aryl sulfonium salt constructed in situ to undergo the Suzuki-Miyaura coupling reaction, so a mono-substituted aromatic hydrocarbon para-arylation or alkenylation product is constructed quickly and efficiently. The method is mild in conditions, high in substrate universality and wide in tolerance of a heterocyclic coupling substrate.
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- Precursors: Synthesis, Reactivity, and Catalytic Application to the Suzuki-Miyaura Reaction
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The complexes (Cy2PC3H6PCy2)Ni(η2-arene) (arene = toluene (3), naphthalene (4)) have been synthesized and studied in detail. Displacement reactions of the toluene ligand afford the complexes (Cy2PC3H6PCy2)Ni(η2-styrene) (5), (Cy2PC3H6PCy2)Ni(PhCN) (6), (Cy2PC3H6PCy2)Ni(CO)2 (7), (Cy2PC3H6PCy2)Ni(PPh3) (8), (Cy2PC3H6PCy2)Ni(PCy3) (9), {(Cy2PC3H6PCy2)Ni}2(μ-H)2 (10), (Cy2PC3H6PCy2)Ni(η2-CO2) (11), and [(Cy2PC3H6PCy2)Ni]2(μ,η2-1,5-COD) (12). The relative rates of ArCl oxidative addition at Ni complexes 3, 4, 6, 8, and 12 have been evaluated experimentally, and the mechanism has been calculated by DFT. Complexes 3 and 4 are efficient catalysts for the Suzuki-Miyaura reaction between chloroarenes and Ar′B(OH)2.
- D'Accriscio, Florian,Ohleier, Alexia,Nicolas, Emmanuel,Demange, Matthieu,Thillaye Du Boullay, Olivier,Saffon-Merceron, Nathalie,Fustier-Boutignon, Marie,Rezabal, Elixabete,Frison, Gilles,Nebra, Noel,Mézailles, Nicolas
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supporting information
p. 1688 - 1699
(2020/06/04)
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- Nickel Carbodicarbene Catalyzes Kumada Cross-Coupling of Aryl Ethers with Grignard Reagents through C–O Bond Activation
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The development of a cross-coupling reaction protocol between aryl ethers and Grignard reagents catalyzed by carbodicarbene (CDC) nickel complexes to afford biaryl compounds through C–O cleavage is reported. Aromatic substrates featuring a broad range of electron neutral, donating, or withdrawing groups are introduced at the desired position. The method has proven effective over a wide range of naphthyl methyl ethers, anisoles, and Grignard reagents. The robustness of the protocol is validated by performing multiple cleavage reactions, gram scale synthesis, and arylation of a dimethoxy esterdiol derivative.
- Ambre, Ram,Yang, Hsuan,Chen, Wen-Ching,Yap, Glenn P. A.,Jurca, Titel,Ong, Tiow-Gan
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p. 3511 - 3517
(2019/08/12)
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- Cellulose supported Pd(II) complex catalyzed carbon-carbon bonds formation
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Corn-cobs are an agro-industrial waste and composed of cellulose mostly. In this study cellulose was isolated from the waste corn-cobs and modified to polymeric hydroxamic acid palladium complex 1 and characterized by using a variety of spectroscopic methods such as field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The complex 1 exhibited high catalytic activity towards Suzuki and Heck coupling reactions of activated and deactivated aryl halides to give the respective coupling products with high yield. Moreover, the complex 1 was recovered and recycled five times with no considerable loss of catalytic overall performance.
- Sarkar, Shaheen M.,Rashid,Karim, Kaykobad Md. Rezaul,Mustapha, Siti Noor Hidayah,Lian, Yuen Mei,Zamri, Normaiza,Khan, Md. Maksudur Rahman,O'Reilly, Emmet J.,Rahman, Md. Lutfor
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p. 2856 - 2861
(2019/01/03)
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- The Hiyama Cross-Coupling Reaction at Parts Per Million Levels of Pd: In Situ Formation of Highly Active Spirosilicates in Glycol Solvents
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A palladium NNC-pincer complex at a 5 mol ppm loading efficiently catalyzed the Hiyama coupling reaction of aryl bromides with aryl(trialkoxy)silanes in propylene glycol to give the corresponding biaryls in excellent yields. This method was applied to the syntheses of adapalene and a biaryl-type liquid-crystalline compound, as well as to the derivatization of dextromethorphan and norfloxacin. ESI-MS and NMR analyses of the reaction mixture suggested the formation of pentacoordinate spirosilicate intermediates in situ. Preliminary theoretical studies revealed that the glycol-derived silicate intermediates formed in situ are quite reactive silicon reagents in the transmetalation step.
- Ichii, Shun,Hamasaka, Go,Uozumi, Yasuhiro
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supporting information
p. 3850 - 3854
(2019/11/11)
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- Bis(dialkylphosphino)ferrocene-Ligated Nickel(II) Precatalysts for Suzuki-Miyaura Reactions of Aryl Carbonates
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Aryl carbonates, a common protecting group in synthetic organic chemistry, are potentially valuable electrophiles in cross-coupling reactions. Here, after performing a thorough evaluation of different precatalysts, we demonstrate that (dcypf)Ni(2-ethylphenyl)(Br) (dcypf = 1,1-bis(dicyclohexylphosphino)ferrocene) is an efficient precatalyst for Suzuki-Miyaura reactions using a variety of aryl carbonates as substrates. Mechanistic studies indicate that (dcypf)Ni(2-ethylphenyl)(Br), which contains a bidentate phosphine that binds in a trans geometry, is an effective precatalyst for these reactions for two reasons: (i) it rapidly forms the Ni(0) active species and (ii) it minimizes comproportionation reactions between the Ni(0) active species and both the unactivated Ni(II) precatalyst and on-cycle Ni(II) complexes to form catalytically inactive Ni(I) species. In contrast, the state of the art precatalyst (dppf)Ni(o-tolyl)(Cl) (dppf = 1,1-bis(diphenylphosphino)ferrocene), which contains a bidentate phosphine that binds in a cis geometry, forms Ni(I) species during activation and is essentially inactive for aryl carbonate couplings. Although the exact reasons on a molecular level why the dcypf system is more active than the dppf system are unclear, our results indicate that in general Ni catalysts supported by the dcypf ligand will give better performance for catalytic reactions involving substrates which undergo relatively slow oxidative addition, such as aryl carbonates.
- Barth, Emily L.,Davis, Ryan M.,Mohadjer Beromi, Megan,Walden, Andrew G.,Balcells, David,Brudvig, Gary W.,Dardir, Amira H.,Hazari, Nilay,Lant, Hannah M. C.,Mercado, Brandon Q.,Peczak, Ian L.
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supporting information
p. 3377 - 3387
(2019/09/30)
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- Superbase-promoted selective carbon-carbon bond cleavage driven by aromatization
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A novel selective carbon-carbon single bond cleavage has been disclosed through the copper-catalyzed reaction of 1-alkyl-3-alkylindolin-2-imine hydrochlorides with substituted 1-(bromomethyl)-2-iodobenzenes leading to fused N-heterocycles. Mechanistic studies showed that the intrinsic drive of aromatization and the action of the superbase derived from sodium tert-butoxide and dimethylsulfoxide were the key factors leading to the carbon-carbon single bond cleavage. Furthermore, the obtained N-heterocycles are indoloquinoline derivatives with wide biological activities.
- Liu, Can,Zhu, Xianjin,Han, Yongzhen,Yang, Haijun,Zhu, Changjin,Fu, Hua
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p. 4984 - 4989
(2019/06/03)
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- Nickel-Catalyzed Kumada Coupling of Boc-Activated Aromatic Amines via Nondirected Selective Aryl C-N Bond Cleavage
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A nickel-catalyzed Kumada coupling of aniline derivatives was developed by selective cleavage of aryl C-N bonds under mild reaction conditions. Without preinstallation of an ortho directing group on anilines, the cross-coupling reactions of Boc-protected aromatic amines with aryl Grignard reagents afforded unsymmetric biaryls. Mechanistic studies by DFT calculations revealed that the nickel-mediated C-N bond cleavage is the rate-limiting step.
- Zhang, Zheng-Bing,Ji, Chong-Lei,Yang, Ce,Chen, Jie,Hong, Xin,Xia, Ji-Bao
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p. 1226 - 1231
(2019/02/14)
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- Dihalogen-bridged NHC-palladium(i) dimers: Synthesis, characterisation and applications in cross-coupling reactions
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A di-iodo-bridged PdI dimer bearing an N-heterocyclic carbene ligand was made accessible via the reduction of [(IPr)PdI2]2 in basic methanol solution. The structural features of [(IPr)PdI]2 were explored by single-crystal X-ray analysis. It was found to be a convenient one-component precatalyst with high activity in Suzuki-Miyaura, Buchwald-Hartwig, and Sonogashira reactions.
- Pirkl, Nico,Del Grosso, Alessandro,Mallick, Bert,Doppiu, Angelino,Goo?en, Lukas J.
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supporting information
p. 5275 - 5278
(2019/05/08)
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- Air-Stable Secondary Phosphine Oxides for Nickel-Catalyzed Cross-Couplings of Aryl Ethers by C-O Activation
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Air- and moisture-stable secondary phosphine oxides (SPOs) enabled nickel-catalyzed Kumada-Corriu cross-couplings of various arylmethyl ethers at room temperature by challenging C-O activation.
- Ghorai, Debasish,Loup, Joachim,Zanoni, Giuseppe,Ackermann, Lutz
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supporting information
p. 429 - 432
(2019/02/26)
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- Thioether–NHC-Ligated PdII Complex for Crafting a Filtration-Free Magnetically Retrievable Catalyst for Suzuki–Miyaura Coupling in Water
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A new benzimidazolium salt, 1-[benzylaminocarbonylmethyl]-3-(2-phenylsulfanylethyl)-1H-benzimidazolium chloride (L), which is a precursor of a novel thioether-functionalized NHC, has been synthesized by subjecting 1H-benzimidazole to a sequence of reactions with 1,2-dichloroethane, sodium thiophenolate, and N-benzyl-2-chloroacetamide, successively. The moisture/air-insensitive complex [Pd(L–HCl)Cl2] (1) was prepared by the reaction of L with PdCl2. The molecular structure of 1, established by X-ray crystallography, revealed a square-planar geometry around Pd. Complex 1 was screened for Suzuki–Miyaura coupling reactions of various aryl/heteroaryl bromides (yields of up to 94 % in 2 h) in water at room temperature. Furthermore, complex 1 was immobilized onto the surface of aminopropyl-functionalized silica-coated magnetite nanoparticles [NPs, Fe3O4@SiO2-(CH2)3-NH2] by a stepwise modification strategy to develop the heterogeneous magnetically retrievable catalyst Fe3O4@SiO2-1′, in which the amide functionality present in the side-arm of the NHC within the NHC–PdII complex serves as linker. This magnetic nanosupport, bearing palladium complexes incorporating a novel thioether-based NHC ligand that functions in aqueous aerobic medium and can be easily separated, renders Fe3O4@SiO2-1′ a most desirable catalyst for the Suzuki–Miyaura coupling reaction. It was also observed that the catalyst was effective for up to seven cycles and was easily separated from the reaction medium by the use of an external magnet, further increasing its appeal.
- Nayan Sharma, Kamal,Satrawala, Naveen,Kumar Joshi, Raj
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p. 1743 - 1751
(2018/05/14)
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- Chromium-Catalyzed Regioselective Kumada Arylative Cross-Coupling of C(aryl)-O Bonds with a Traceless Activation Strategy
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We report here the chromium-catalyzed regioselective Kumada arylative cross-coupling of C(aryl)-O bonds at ambient temperature. By using a simple and low-cost chromium(II) chloride salt as a precatalyst, accompanied by a 2-pyridyl ligation, the catalytic cleavage and arylative coupling of C(aryl)-O bonds were achieved with a traceless activation strategy, overcoming the regioselectivity obstacle when several C-O bonds coexist in the Kumada coupling system.
- Fan, Fei,Tang, Jinghua,Luo, Meiming,Zeng, Xiaoming
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p. 13549 - 13559
(2018/10/31)
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- Ni-Catalyzed Cross-Coupling of Dimethyl Aryl Amines with Arylboronic Esters under Reductive Conditions
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Herein, we reported a successful Suzuki-Miyaura coupling of dimethyl aryl amines to forge biaryl skeleton via Ni catalysis in the absence of directing groups and preactivation. This transformation proceeded with high efficiency in the presence of magnesium. Preliminary mechanism studies demonstrated dual roles of magnesium: (i) a reductant that reduced Ni(II) species to active Ni(I) catalyst; (ii) a unique promoter that facilitated the Ni(I)/Ni(III) catalytic cycle.
- Cao, Zhi-Chao,Xie, Si-Jun,Fang, Huayi,Shi, Zhang-Jie
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supporting information
p. 13575 - 13579
(2018/10/24)
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- Methylation of Arenols through Ni-catalyzed C—O Activation with Methyl Magnesium Bromide
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Direct alkylation of arenols with alkyl organometallic reagents has never been approached. Herein we reported the first successful example of nickel-catalyzed methylation of arenols with methyl Grignard reagents to construct C(sp2)-C(sp3/
- Shi, Wen-Juan,Shi, Zhang-Jie
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supporting information
p. 183 - 186
(2018/01/15)
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- Less hindered ligands give improved catalysts for the nickel catalysed Grignard cross-coupling of aromatic ethers
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The challenging reaction of unactivated ortho-substituted aromatic ethers with Grignard reagents has been found to be most effectively catalysed using nickel complexes of less sterically hindered ligands. Air stable, cheap, commercially available [NiCl2(PnBu3)2] stands out as an improved catalyst for this type of transformation. The improved results with this catalyst even extend to some couplings of a more activated substrate when examined at higher temperatures and at catalyst loadings down to 0.1 mol%. Unusual induction periods in these latter reactions have been related to the by-product magnesium salts acting as co-catalysts.
- Harkness, Gavin J.,Clarke, Matthew L.
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p. 328 - 334
(2018/01/12)
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- Combined Theoretical and Experimental Studies of Nickel-Catalyzed Cross-Coupling of Methoxyarenes with Arylboronic Esters via C-O Bond Cleavage
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Nickel(0)-catalyzed cross-coupling of methoxyarenes through C-O bond activation has been the subject of considerable research because of their favorable features compared with those of the cross-coupling of aryl halides, such as atom economy and efficiency. In 2008, we have reported nickel/PCy3-catalyzed cross-coupling of methoxyarenes with arylboronic esters in which the addition of a stoichiometric base such as CsF is essential for the reaction to proceed. Recently, we have also found that the scope of the substrate in the Suzuki-Miyaura-type cross-coupling of methoxyarenes can be greatly expanded by using 1,3-dicyclohexylimidazol-2-ylidene (ICy) as the ligand. Interestingly, a stoichiometric amount of external base is not required for the nickel/ICy-catalyzed cross-coupling. For the mechanism and origin of the effect of the external base to be elucidated, density functional theory calculations are conducted. In the nickel/PCy3-catalyzed reactions, the activation energy for the oxidative addition of the C(aryl)-OMe bond is too high to occur under the catalytic conditions. However, the oxidative addition process becomes energetically feasible when CsF and an arylboronic ester interact with a Ni(PCy3)2/methoxyarene fragment to form a quaternary complex. In the nickel/ICy-catalyzed reactions, the oxidative addition of the C(aryl)-OMe bond can proceed more easily without the aid of CsF because the nickel-ligand bonds are stronger and therefore stabilize the transition state. The subsequent transmetalation from an Ar-Ni-OMe intermediate is determined to proceed through a pathway with lower energies than those required for β-hydrogen elimination. The overall driving force of the reaction is the reductive elimination to form the carbon-carbon bond.
- Schwarzer, Martin C.,Konno, Ryosuke,Hojo, Takayuki,Ohtsuki, Akimichi,Nakamura, Keisuke,Yasutome, Ayaka,Takahashi, Hiroaki,Shimasaki, Toshiaki,Tobisu, Mamoru,Chatani, Naoto,Mori, Seiji
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supporting information
p. 10347 - 10358
(2017/08/10)
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- Cyclopalladation in the Periphery of a NHC Ligand as the Crucial Step in the Synthesis of Highly Active Suzuki–Miyaura Cross-Coupling Catalysts
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Starting from 2,4-dichloropyrimidine, 4-(2-dialkylamino)pyrimidinyl functionalized mesitylimidazolium chlorides are accessible in a five-step reaction sequence. Two routes leading to palladium NHC complexes derived from these ligands have been worked out: By transmetalation with the corresponding NHC-AgCl complexes, C,N-coordinated palladium(II) complexes can be obtained. Treatment of palladium dichloride with the imidazolium salts in pyridine and in the presence of K2CO3 gives cyclometalated and thus C,C-coordinated compounds. The reactivities of all these compounds were investigated in detail as well as their performance in the catalytic Suzuki–Miyaura cross-coupling reaction. It turned out that the C,C-coordinated derivatives exhibit high catalytic activities in the coupling of arylboronic acids with aryl chlorides, which is consistent with the generally accepted mechanistic ideas on substrate activation.
- Fizia, Agnes,Gaffga, Maximilian,Lang, Johannes,Sun, Yu,Niedner-Schatteburg, Gereon,Thiel, Werner R.
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p. 14563 - 14575
(2017/10/07)
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- Cyclobutene vs 1,3-Diene Formation in the Gold-Catalyzed Reaction of Alkynes with Alkenes: The Complete Mechanistic Picture
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The intermolecular gold(I)-catalyzed reaction between arylalkynes and alkenes leads to cyclobutenes by a [2 + 2] cycloaddition, which takes place stepwise, first by formation of cyclopropyl gold(I) carbenes, followed by a ring expansion. However, 1,3-butadienes are also formed in the case of ortho-substituted arylalkynes by a metathesis-type process. The corresponding reaction of alkenes with aryl-1,3-butadiynes, ethynylogous to arylalkynes, leads exclusively to cyclobutenes. A comprehensive mechanism for the gold(I)-catalyzed reaction of alkynes with alkenes is proposed on the basis of density functional theory calculations, which shows that the two pathways leading to cyclobutenes or dienes are very close in energy. The key intermediates are cyclopropyl gold(I) carbenes, which have been independently generated by retro-Buchner reaction from stereodefined 1a,7b-dihydro-1H-cyclopropa[a]naphthalenes.
- De Orbe, M. Elena,Amenós, Laura,Kirillova, Mariia S.,Wang, Yahui,López-Carrillo, Verónica,Maseras, Feliu,Echavarren, Antonio M.
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supporting information
p. 10302 - 10311
(2017/08/09)
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- Nickel-mediated decarbonylation of simple unstrained ketones through the cleavage of carbon-carbon bonds
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Despite advances in methods for the decarbonylation of aldehydes, the decarbonylation of ketones has been met with limited success because this process requires the activation of two inert carbon-carbon bonds. All of the decarbonylation reactions of simple unstrained ketones reported to date require the addition of a stoichiometric rhodium complex. We report herein the nickel/N-heterocyclic carbene-mediated decarbonylation of simple diaryl ketones. This reaction shows unique acceleration effects based on the presence of both electron-donating and electron-withdrawing groups.
- Morioka, Toshifumi,Nishizawa, Akihiro,Furukawa, Takayuki,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 1416 - 1419
(2017/02/10)
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- Amide-ligand-controlled highly para-selective arylation of monosubstituted simple arenes with arylboronic acids
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Pd-catalyzed highly para-selective arylations of monosubstituted simple arenes with arylboronic acids to widely existed biaryls have been developed. Inspired by requisite amide-directing groups in reported selective oxidative couplings, amide ligands, especially DMF, are designed and found to be critical for the selectivity control in current arylations.
- Luan, Yu-Xin,Zhang, Tao,Yao, Wei-Wei,Lu, Ke,Kong, Lu-Yao,Lin, Yu-Tong,Ye, Mengchun
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supporting information
p. 1786 - 1789
(2017/02/15)
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- Magnetically water-dispersible and recoverable rhodium organometallic catalyst derived from Wilkinson's catalyst for promoting organic reactions
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A novel magnetic rhodium catalyst was prepared through immobilizing Wilkinson's catalyst on the surface of silica-coated iron oxide nanoparticles. After (thio)diphenylphosphine (─S─PPh2) was modified on the surface of the silica-coated iron oxide nanoparticles, tris(triphenylphosphine)rhodium(I) chloride was employed to synthesize the Rh(Cl)(PPh3)2(Ph2P─S─) complex, affording a rhodium loading of 0.16?mmol?g?1. The Rh(I) organometallic magnetic nanoparticles form a novel class of heterogeneous catalyst which is particularly suitable for the practice of organic synthesis. The prepared system exhibits high catalytic efficiency in Suzuki–Miyaura and Miyaura–Michael reactions in ethanol–water solution. High yield, low reaction times, use of green solvents and non-toxicity of the catalyst are the main merits of this protocol. Also, magnetic separation is an environmentally friendly alternative for the recovery of the catalyst, since it minimizes energy and catalyst loss by preventing mass loss and oxidation. The produced catalyst was characterized using a variety of techniques.
- Nejat, Razieh,Mahjoub, Alireza
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- Practical Cross-Coupling between O-Based Electrophiles and Aryl Bromides via Ni Catalysis
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Cross-coupling of various O-based electrophiles with aryl bromides was developed through Ni-catalyzed C-O activation in the presence of magnesium. Beside carboxylates, carbamates, and ethers, phenols exhibited excellent reactivity under modified conditions. This chemistry was featured as a simple and environmentally benign process with low catalyst loading and easy manipulations. The method exhibited broad substrate scopes.
- Cao, Zhi-Chao,Luo, Qin-Yu,Shi, Zhang-Jie
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supporting information
p. 5978 - 5981
(2016/12/09)
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- Cross-Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C?O or C?N Bond Cleavage
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Various aryl-, alkenyl-, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross-coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5-cyclooctadiene) catalysts with N-heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot.
- Yang, Ze-Kun,Wang, Dong-Yu,Minami, Hiroki,Ogawa, Hiroyuki,Ozaki, Takashi,Saito, Tatsuo,Miyamoto, Kazunori,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 15693 - 15699
(2016/10/25)
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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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- Nickel- or Iron-Catalyzed Cross-Coupling of Aryl Carbamates with Arylsilanes
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Aryl carbamates were for the first time applied as electrophiles in the cross-coupling with arylsilanes via nickel or iron catalysis to construct valuable biaryl compounds. This new coupling reaction features a good group tolerance and non-sensitivity to steric hindrance on both aryl carbamates and arylsilanes. (Figure presented.).
- Shi, Wen-Juan,Zhao, Hong-Wei,Wang, Yang,Cao, Zhi-Chao,Zhang, Li-Sheng,Yu, Da-Gang,Shi, Zhang-Jie
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supporting information
p. 2410 - 2416
(2016/08/16)
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- Palladium catalyzed desulfinylative couplings between aryl sulfinates and aryl bromide/iodide for the synthesis of biaryls
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We have synthesized biaryls from the coupling reaction between aryl sulfinates and aryl halides using homogeneous palladium catalytic system. The developed method is simple and efficient. These methodologies are particularly useful to prepare symmetrical as well as unsymmetrical biaryls with excellent product yield. The suggested protocol demonstrated a broad substrate scope.
- Gund, Sitaram Haribhau,Balsane, Kishor Eknath,Nagarkar, Jayashree Milind
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p. 5051 - 5056
(2016/07/25)
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- Synthesis of Biaryls through Nickel-Catalyzed Suzuki-Miyaura Coupling of Amides by Carbon-Nitrogen Bond Cleavage
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The first Ni-catalyzed Suzuki-Miyaura coupling of amides for the synthesis of widely occurring biaryl compounds through N-C amide bond activation is reported. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents on both coupling partners. The reaction constitutes the first example of the Ni-catalyzed generation of aryl electrophiles from bench-stable amides with potential applications for a broad range of organometallic reactions. Breaking and making: The first nickel-catalyzed Suzuki-Miyaura coupling of amides for the synthesis of biaryl compounds through N-C amide bond cleavage is reported. The reaction tolerates a wide range of sensitive and electronically diverse substituents on both coupling partners.
- Shi, Shicheng,Meng, Guangrong,Szostak, Michal
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p. 6959 - 6963
(2016/06/13)
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- Of the three-ring-containing nitrogen heterocyclic shan Lindancabeen nickelhexyl phosphine (II) complex and application thereof
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The invention discloses a complex and application of monophosphine monoazacyclo-carben nickel containing tricyclic hexyl phosphine. The molecular formula of the complex of the monophosphine monoazacyclo-carben nickel is (PCy3)Ni[(RNCHCHNR)C]X2; in the molecular formula, the PCy3 is tricyclic hexyl phosphine; the R is tertiary butyl, 2,6-diisopropyl phenyl or mesitylene; the X is chlorine or bromine. The complex of monophosphine monoazacyclo-carben nickel containing tricyclic hexyl phosphine is simple to prepare, easy to operate, easy in purification of products and high in yield, can stably exist in air, and can efficiently catalyze cross coupling reaction of aryl methyl ether and aryl Grignard reagent.
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Paragraph 0061; 0062
(2017/02/28)
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- The Missing C1-C5 Cycloaromatization Reaction: Triplet State Antiaromaticity Relief and Self-Terminating Photorelease of Formaldehyde for Synthesis of Fulvenes from Enynes
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The last missing example of the four archetypical cycloaromatizations of enediynes and enynes was discovered by combining a twisted alkene excited state with a new self-terminating path for intramolecular conversion of diradicals into closed-shell products. Photoexcitation of aromatic enynes to a twisted alkene triplet state creates a unique stereoelectronic situation, which is facilitated by the relief of excited state antiaromaticity of the benzene ring. This enables the usually unfavorable 5-endo-trig cyclization and merges it with 5-exo-dig closure. The 1,4-diradical product of the C1-C5 cyclization undergoes internal H atom transfer that is coupled with the fragmentation of an exocyclic C-C bond. This sequence provides efficient access to benzofulvenes from enynes and expands the utility of self-terminating aromatizing enyne cascades to photochemical reactions. The key feature of this self-terminating reaction is that, despite the involvement of radical species in the key cyclization step, no external radical sources or quenchers are needed to provide the products. In these cascades, both radical centers are formed transiently and converted to the closed-shell products via intramolecular H-transfer and C-C bond fragmentation. Furthermore, incorporating C-C bond cleavage into the photochemical self-terminating cyclizations of enynes opens a new way for the use of alkenes as alkyne equivalents in organic synthesis.
- Mohamed, Rana K.,Mondal, Sayantan,Jorner, Kjell,Delgado, Thais Faria,Lobodin, Vladislav V.,Ottosson, Henrik,Alabugin, Igor V.
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p. 15441 - 15450
(2015/12/26)
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- Catalytic Decarboxylative Cross-Coupling of Aryl Chlorides and Benzoates without Activating ortho Substituents
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The restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates was overcome by holistic optimization of a bimetallic Cu/Pd catalyst system. The combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern. Lifting the restriction: A combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern (see scheme; FG=functional group). This approach lifts the restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates.
- Tang, Jie,Biafora, Agostino,Goossen, Lukas J.
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supporting information
p. 13130 - 13133
(2015/11/02)
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- Pincer-Nickel-Catalyzed Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides
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The nickel N,N,N-pincer complex 2 was demonstrated to effectively catalyze the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups. A nickel N,N,N-pincer complex effectively catalyzes the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups.
- Tao, Jian-Long,Wang, Zhong-Xia
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p. 6534 - 6540
(2015/10/19)
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- Triarylphosphines as Aryl Donors for Pd(II)-Catalyzed Aromatic Coupling of Oxabenzonorbornadienes
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A new approach was developed for Pd(II)-catalyzed aromatic coupling of oxabenzonorbornadienes with triarylphosphines as both ligands and aryl donors. Diverse functional groups including halo- (F-, Cl-, and Br-), CF3-, and furyl groups are well tolerated. For unsymmetrical triarylphosphines, the migration ability of aryls is consistent with the electronic property of substituents and maintains the order EDG-Ar > H-Ar > EWD-Ar (EDG means electron-donating group, EWG means electron-withdrawing group). A preliminary mechanistic study was also disclosed.
- Zhou, Hui,Li, Jixing,Yang, Huameng,Xia, Chungu,Jiang, Gaoxi
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supporting information
p. 4628 - 4631
(2015/09/28)
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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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p. 4484 - 4489
(2015/03/30)
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- Alkenes as alkyne equivalents in radical cascades terminated by fragmentations: Overcoming stereoelectronic restrictions on ring expansions for the preparation of expanded polyaromatics
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Chemoselective interaction of aromatic enynes with Bu3Sn radicals can be harnessed for selective cascade transformations, yielding either Sn-substituted naphthalenes or Sn-indenes. Depending on the substitution at the alkene terminus, the initial regioselective 5-exo-trig cyclizations can be intercepted at the 5-exo stage via either hydrogen atom abstraction or C-S bond scission or allowed to proceed further to the formal 6-endo products via homoallylic ring expansion. Aromatization of the latter occurs via β-C-C bond scission, which is facilitated by 2c,3e through-bond interactions, a new stereoelectronic effect in radical chemistry. The combination of formal 6-endo-trig cyclization with stereoelectronically optimized fragmentation allows the use of alkenes as synthetic equivalents of alkynes and opens a convenient route to α-Sn-substituted naphthalenes, a unique launching platform for the preparation of extended polyaromatics.
- Mohamed, Rana K.,Mondal, Sayantan,Gold, Brian,Evoniuk, Christopher J.,Banerjee, Tanmay,Hanson, Kenneth,Alabugin, Igor V.
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supporting information
p. 6335 - 6349
(2015/06/02)
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- Organoaluminum-Mediated Direct Cross-Coupling Reactions
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We present a direct cross-coupling reaction between arylaluminum compounds (ArAlMe2·LiCl) and organic halides RX (R=aryl, alkenyl, alkynyl; X=I, Br, and Cl) without any external catalyst. The reaction takes place smoothly, simply upon heating, thereby enabling the efficient and chemo-/stereoselective formation of biaryl, alkene, and alkyne coupling products with broad functional group compatibility.
- Minami, Hiroki,Saito, Tatsuo,Wang, Chao,Uchiyama, Masanobu
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p. 4665 - 4668
(2015/04/14)
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- Pd-functionalized MCM-41 nanoporous silica as an efficient and reusable catalyst for promoting organic reactions
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Pd-functionalized MCM-41 nanoporous silica has been explored as an efficient and recyclable catalyst to effect Suzuki and Mizoroki-Heck cross-coupling reactions, under various conditions. In Suzuki-Miyaura reactions, various aryl halides were coupled with aryl boronic acids at 100 °C under solvent-free conditions using K2CO3 as base and the maximum Ar-Ar yield reached 95%. The MCM(Pd)-41 catalyst was also used for a good range of Heck reactions using different aryl halides with styrene or n-butyl acrylate esters at 130 °C under solvent-free conditions using n-Pr3N as base that gave the maximum yields of 95% and 92%, respectively. High yield, low reaction times, non-toxicity and recyclability of the catalyst are the main merits of this protocol. The catalyst has been characterized by FT-IR, XRD, SEM, TEM, XPS, EDX, ICP-AES, TG and N2 adsorption-desorption.
- Nejat, Razieh,Mahjoub, Ali Reza,Hekmatian, Zahra,Azadbakht, Tahereh
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p. 16029 - 16035
(2015/02/19)
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- Mixed NHC/Phosphine Ni(II) Complexes: Synthesis and Their Applications as Versatile Catalysts for Selective Cross-Couplings of ArMgX with Aryl Chlorides, Fluorides, and Methyl Ethers
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New methods for the preparation of mixed NHC/phosphine Ni(II) complexes have been developed. It was shown that the quaternary ammonium cation in the easily available Ni(II) complexes [NEt4][Ni(PPh3)X3] (X = Cl and Br) can act as a good leaving group in reactions of [NEt4][Ni(PPh3)X3] with the bulky ItBu (ItBu = 1,3-ditertbutylimidazol-2-ylidene) or IPr [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] ligand, resulting in the corresponding mixed NHC/PPh3 Ni(II) complexes Ni(PPh3)(ItBu)X2 (X = Cl, 1; X = Br, 2) or Ni(PPh3)(IPr)Br2 (3) in high yields. The PPh3 ligand in these obtained mixed NHC/PPh3 Ni(II) complexes can be easily substituted by a more electron-donating phosphine ligand, i.e., PCy3, resulting in the corresponding mixed NHC/PCy3 Ni(II) complexes Ni(PCy3)(ItBu)Br2 (4) and Ni(PCy3)(IPr)Br2 (5) in high yields. The crystal structures of these Ni(II) complexes have been characterized, which revealed a trans disposition of the NHC ligand to the phosphine ligand. The catalytic behaviors of them on varying the carbene ligand (ItBu vs IPr) as well as the phosphine ligand (PPh3 vs PCy3) were investigated in the cross-coupling of aryl Grignard reagents with a wide range of electrophiles. In addition to a significant synergic effect on their catalytic activities, high selectivity for the activation and transformation of C-Cl, C-F and C-O bonds was achieved based on the rational structural design. Complex 2 showed the highest catalytic activity for the cross-coupling of aryl chlorides and fluorides with aryl Grignard reagents, but exhibit little activity for the cross-coupling of aryl methyl ethers with aryl Grignard reagents. On contrast, complex 4 showed great potential for the aryl methyl ethers involved cross-coupling reactions, although its reactivity for the activation of the C-X bond is very poor. The difference in catalytic activity between 2 and 4 has been successfully employed to construct oligoarenes by selective cross-coupling reactions.
- Zhang, Jie,Xu, Jin,Xu, Yanchao,Sun, Hongmei,Shen, Qi,Zhang, Yong
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p. 5792 - 5800
(2016/01/12)
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- Nickel-catalysed Suzuki-Miyaura cross-coupling reactions of aryl halides with arylboronic acids in ionic liquids
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An efficient strategy for the nickel-catalysed synthesis of biaryls and terphenyls has been developed in environmentally-friendly reaction media. In the presence of β-diketone and PPh3 ligands, Ni(TFA)2 acted as an effective catalyst for the Suzuki-Miyaura cross-coupling of aryl halides and arylboronic acids in an ionic liquid solution. Biaryls and terphenyls were obtained in good yields under this catalytic system.
- Wang, Man,Yuan, Xiaobin,Li, Hongyu,Ren, Limin,Sun, Zhizhong,Hou, Yanjun,Chu, Wenyi
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supporting information
p. 154 - 157
(2015/02/19)
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- Improved procedure for single-electron-transfer-induced grignard cross-coupling reaction
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Aryl Grignard reagents were found to undergo coupling with aryl or alkenyl bromides in the presence of LiCl in a mixed solvent consisting of toluene and THF (2/1). Previously employed removal of THF with evacuation from Grignard solutions is no longer needed to obtain biaryls and styrene derivatives.
- Shirakawa, Eiji,Okura, Keisho,Uchiyama, Nanase,Murakami, Takuya,Hayashi, Tamio
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supporting information
p. 922 - 924
(2014/06/23)
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