- Palladium-catalyzed cross-coupling of 2,3-naphthoxadisilole with aryl halides
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Palladium-catalyzed cross-coupling between 2,3-naphthoxadisilole and aryl halides in the presence of tetrabutylammonium fluoride afforded 2-aryl naphthalenes. This is first report that oxadisilole served as a partner in the palladium-catalyzed cross-coupling reactions. The reaction mechanism was also studied.
- Ding, Han,Chen, Yali,Cao, Weiguo,Wu, Kaicheng,Chen, Jie,Lee, Albert W. M.
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- Phosphine-free palladium(II)-catalyzed arylation of naphthalene and benzene with aryl iodides
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(Chemical Equation Presented) A phosphine-free arylation of naphthalene and benzene with aryl iodides to give biaryls in moderate to good yields is carried out in the presence of catalytic Pd(OAc)2 and stoichiometric CF 3CO2 Ag in TFE or/and TFA.
- Qin, Chunxia,Lu, Wenjun
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- The suzuki-miyaura reaction performed using a palladium-n-heterocyclic carbene catalyst and a weak inorganic base
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N-Heterocyclic carbenes (NHCs) have been shown to be useful ligands for the Suzuki-Miyaura cross-coupling at low catalyst loadings. We now report that the commercially available and air-stable [Pd(IPr)(cin)Cl] pre-catalyst permits the formation of various functionalized biaryls from aryl chlorides and boronic acids (37 examples) under very mild conditions using a mixture of ethanol/water as solvent and an inorganic base. [Pd(IPr)(cin)Cl] permits an operationally simple Suzuki-Miyaura reaction under very mild conditions using a mixture of ethanol/water as solvent and an inorganic base.
- Izquierdo, Frédéric,Corpet, Martin,Nolan, Steven P.
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- Palladium-Catalyzed Stereoselective Reductive Coupling Reactions of Organic Halides with 7-Heteroatom Norbornadienes
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Organic halides react with 7-heteroatom benzonorbornadiene derivatives 1 - 4 in the presence of Pd(PPh3)2Cl2 and zinc powder to give cis-1,2-dihydro-1-naphthol or methyl N-(cis-1,2-dihydro-1-naphthol)carbamate derivatives stereoselectively.
- Duan, Jiun-Pey,Cheng, Chien-Hong
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- 3,3'-((Arylmethylene)bis(4-methoxy-3,1-phenylene)) dipyridine derivatives as convenient ligands for Suzuki–Miyaura chemo- and homoselective cross-coupling reactions
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Four novel N,N-bidentate triarylmethane-based ligands bearing β-pyridyl residues have been prepared and the catalytic activity of their in-situ generated palladium complexes were studied in the Suzuki–Miyaura cross-coupling reactions. Air and moisture stable 3,3'-((arylmethylene)bis(4-methoxy-3,1-phenylene))dipyridines L1-3 showed excellent activity in the Suzuki coupling reactions of aryl halides with aryl boronic acids under thermal and sonochemical reaction conditions. The described methodology provided good to high yields in short reaction times at ambient conditions. Moreover, it offered a straightforward way for Suzuki–Miyaura chemo- and homoselective cross-coupling of aryl halides with phenyl boronic acid. The structures of synthesized compounds were fully characterized by FT-IR, 1H-NMR, 13C-NMR, and elemental analyses. The coordination of palladium acetate to nitrogen sites of L1 was also studied using FTIR spectroscopy, EDX analysis and SEM observations. Graphic abstract: The in-situ generated Pd-complexes of N,N-bidentate ligands L1-3 are described as robust and highly effective catalytic systems for the Suzuki cross-coupling of aryl halides with aryl boronic acids under thermal and sonochemical reaction conditions.[Figure not available: see fulltext.]
- Hosseini, Raziyeh,Mohammadiannejad, Kazem,Ranjbar-Karimi, Reza
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- Desulfurization of Diaryl(heteroaryl) Sulfoxides with Benzyne
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Two benzyne-enabled desulfurization reactions have been demonstrated which convert diaryl sulfoxides and heteroaryl sulfoxides to biaryls and desulfurized heteroarenes, respectively. The reaction accessing biaryls tolerates a variety of functional groups, such as halides, pseudohalides, and carbonyls. Mechanistic studies reveal that both reactions proceed via a common assembly process but divergent disassemblies of the generated tetraaryl(heteroaryl) sulfuranes.
- Chen, De-Li,Sun, Yan,Chen, Mengyuan,Li, Xiaojin,Zhang, Lei,Huang, Xin,Bai, Yihui,Luo, Fang,Peng, Bo
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supporting information
(2019/06/13)
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- Highly active and reusable hydrotalcite-supported Pd(0) catalyst for Suzuki coupling reactions of aryl bromides and chlorides
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A palladium(0) nanocluster supported on hydrotalcite has been prepared and tested for the Suzuki coupling reaction. The prepared catalyst showed very efficient catalytic activity for cross coupling of iodo- and bromoarenes under very mild reaction conditions, affording >90% yield. Under the optimized reaction conditions, chloroarenenes also showed very good reactivity. Transmission electron microscopic imaging data showed the formation of very small Pd(0)-nanoclusters (d = 2.2 ± 0.5 nm) well dispersed on the support, which enhanced the activity and stability of the catalyst for the Suzuki cross-coupling reaction. This catalytic system offers an easy method of preparation with good activity and reusability up to five cycles.
- Karanjit, Sangita,Kashihara, Masaya,Nakayama, Atsushi,Shrestha, Lok Kumar,Ariga, Katsuhiko,Namba, Kosuke
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supporting information
p. 948 - 954
(2018/01/27)
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- Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-aminopyridine
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One palladium dichloride adduct of a phosphine-pyridine ligand N-diphenylphosphanyl-2-aminopyridine (L1) [(L1)PdCl2] (1) has been prepared and structurally characterized. Compound 1 can be used as an effective catalyst for the Suzuki-Miyaura cross-coupling reactions of unreactive aryl chlorides with aryl boronic acids, and worked much better than its mono- or bidentate phosphine ligands. The reactions with a wide scope of substrates proceeded to give desired products in good to excellent yields.
- Xu, Lin-Yan,Liu, Chun-Yu,Liu, Shi-Yuan,Ren, Zhi-Gang,Young, David James,Lang, Jian-Ping
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p. 3125 - 3132
(2017/05/08)
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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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- 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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- Synthesis and isolation of an acyclic tridentate bis(pyridine)carbodicarbene and studies on its structural implications and reactivities
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The simple synthetic development of acyclic pincer bis(pyridine)carbodicarbene is depicted herein. Presented is the first isolated structural pincer carbodicarbene with a C-C-C angle of 143°, larger than the monodentate framework. More importantly, theore
- Hsu, Yu-Chen,Shen, Jiun-Shian,Lin, Bo-Chao,Chen, Wen-Ching,Chan, Yi-Tsu,Ching, Wei-Min,Yap, Glenn P. A.,Hsu, Chao-Ping,Ong, Tiow-Gan
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supporting information
p. 2420 - 2424
(2015/02/19)
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- Nickel-catalyzed one-pot Suzuki-Miyaura cross-coupling of phenols and arylboronic acids mediated by N,N-ditosylaniline
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An efficient method for the construction of two distinct C aryl-Caryl bonds through the Ni-catalyzed Suzuki-Miyaura cross-coupling of phenols with arylboronic acids has been developed. This reaction proceeds through the in situ tosylation of phenols by using N,N-ditosylaniline as the sulfonylating reagent, which is highly active, markedly stable, and easily prepared. The scope with respect to the coupling partners - phenols and boronic acids - is broad, and sensitive functional groups are tolerated. Phenols, especially those containing an unprotected amino group, which are generally problematic for coupling under conventional one-pot conditions, are also viable substrates in this transformation.
- Chen, Liangshun,Lang, Hongyue,Fang, Lei,Zhu, Mengyun,Liu, Jinqian,Yu, Jianjun,Wang, Limin
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supporting information
p. 4953 - 4957
(2014/08/18)
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- Efficient PdCl2-catalyzed Suzuki reactions using simple dicationic imidazolium salts as ligands in aqueous DMF
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Three new palladium catalysts, prepared via reactions of PdCl2 with readily obtained and inexpensive dicationic imidazolium salts, have been developed for the Suzuki reaction. The pre-catalyst was formed in situ using the imidazolium ligand, ba
- Huang, Qing,Qiu, Jiabin,Li, Limei,Xu, Guohai,Zhou, Zhonggao
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p. 661 - 665
(2014/08/18)
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- Platinum-catalyzed C-H arylation of simple arenes
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This report describes the Na2PtCl4 catalyzed C-H arylation of arene substrates with diaryliodonium salts. The site selectivity of these reactions is predominantly controlled by steric factors. Remarkably, Na2PtCl4-catalyzed naphthalene arylation proceeds with opposite site selectivity compared to that obtained with Na2PdCl 4 as the catalyst. Preliminary mechanistic studies provide evidence for a PtII/PtIV catalytic cycle involving rate-limiting C-C bond-forming reductive elimination.
- Wagner, Anna M.,Hickman, Amanda J.,Sanford, Melanie S.
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supporting information
p. 15710 - 15713
(2013/11/06)
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- Palladium-catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids
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Readily available NHC-Pd(ii)-Mp complexes 2 showed efficient catalytic activity toward the Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the expected coupling products in good to high yields.
- Wang, Zhan-Yong,Ma, Qin-Na,Li, Ren-Hao,Shao, Li-Xiong
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p. 7899 - 7906
(2013/11/19)
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- A deacetylation-diazotation-coupling sequence: Palladium-catalyzed C-C bond formation with acetanilides as formal leaving groups
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Acetanilides can be deacetylated and diazotized in situ, and subsequently used in Pd-catalyzed coupling reactions without isolation of the diazonium intermediate. Heck reactions, Suzuki crosscoupling reactions, and a Pd-catalyzed [2+2+1] cycloaddition hav
- Schmidt, Bernd,Berger, Rene
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supporting information
p. 463 - 476
(2013/05/08)
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- P,N-Type benzimidazolyl phosphine ligands for the palladium-catalyzed Suzuki coupling of potassium aryltrifluoroborates and aryl chlorides
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This study describes the efficacy of P,N-type benzimidazolyl phosphine ligands, which can be easily synthesized from commercially available and inexpensive starting materials. The application of this ligand array in palladium-catalyzed Suzuki-Miyaura coupling reaction of aryl chlorides with potassium aryltrifluoroborates is described. The air stable benzimidazolyl phosphines in combination with a palladium metal precursor provides highly effective catalysts for the Suzuki-Miyaura coupling of unactivated aryl chlorides and can achieve a catalyst loading of only 0.05 mol %.
- Wong, Shun Man,So, Chau Ming,Chung, Kin Ho,Luk, Chi Him,Lau, Chak Po,Kwong, Fuk Yee
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scheme or table
p. 3754 - 3757
(2012/09/25)
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- C,N-palladacycles containing N-heterocyclic carbene and azido ligands - Effective catalysts for Suzuki-Miyaura cross-coupling reactions
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Azido-palladacycles containing C,N-donor and N-heterocyclic carbene ligands, [(C,N-L)Pd(N3)(NHC)] [NHC = IPr; 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene], were prepared from (i) IPr and dinuclear PdII azides, [Pd(μ-N3)(C,N-Ln)]2 [C,N-L1H = N,N′-dimethylbenzylamine; C,N-L2H = 2-(2′-thienyl)pyridine; C,N-L3H = azobenzene; C,N-L 4H = 2-(p-tolyl)pyridine], or from (ii) NaN3 and mononuclear PdII chloride, [Pd(Cl)(IPr)(C,N-Ln)], in aqueous solution. The structures of two of these products were determined by X-ray crystallography. The palladacycles showed high catalytic efficiency toward activated and nonactivated aryl bromides (at room temperature) as well as aryl chlorides (at 80 C) in Suzuki-Miyaura cross-coupling reactions. In addition, coupling reactions of aryl chlorides using potassium aryl trifluoroborates instead of phenyl boronic acid gave good-to-excellent product yields. Suzuki-Miyaura cross-coupling reactions of aryl bromides and chlorides with organoboronic acid as well as potassium aryl trifluoroborates catalyzed by C,N-donor palladacycles containing N-heterocyclic carbene (NHC) and azido ligands under various conditions have been performed. Copyright
- Kim, Yong-Joo,Lee, Jung-Hyun,Kim, Taejung,Ham, Jungyeob,Zheng, Zhen Nu,Lee, Soon W.
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p. 6011 - 6017
(2013/03/14)
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- Benzotriazol-1-ylmethanol: An excellent bidentate ligand for the copper/palladium-catalyzed C-N and C-C coupling reaction
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An efficient benzotriazole based N,O bidentate ligands for the Cu-catalyzed N-arylation of π-excessive nitrogen heterocycles is described. This ligand accomplishes C-N coupling of Nheterocycles and C-C coupling of boronic acids with a variety of hindered, functionalized aryl/heteroaryl halides under mild reaction conditions in good to excellent yields. Using his ligand C-N and C-C (Suzuki) couplings with bromoarenes could be conducted with less catalyst loading. A wide array of deactivated and hindered aryl halides react cleanly to afford the functionalized biaryl derivatives in high yields. ARKAT-USA, Inc.
- Jha, Rajeev R.,Singh, Jaspal,Tiwari, Rakesh K.,Verma, Akhilesh K.
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p. 228 - 248
(2013/02/23)
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- Benzotriazole: An efficient, inexpensive and phosphine-free ligand for the palladium-catalyzed Suzuki-Miyaura reaction
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Benzotriazole has been disclosed as an efficient and inexpensive ligand for the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction of arylhalides with arylboronic acids. This preparative convenient system afforded the corresponding coupling products, biaryls and terphenyls in good to excellent yields.
- Jha, Rajeev Ranjan,Chaudhary, Ritu,Chandra, Ramesh,Verma, Akhilesh Kumar
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experimental part
p. 1187 - 1194
(2012/04/04)
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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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- A robust hydrophilic pyridine-bridged bis-benzimidazolylidene palladium pincer complex: Synthesis and its catalytic application towards Suzuki-Miyaura couplings in aqueous solvents
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A novel hydrophilic pyridine-bridged bis-benzimidazolylidene palladium pincer complex (3) acted as a highly efficient robust recyclable molecular catalyst towards Suzuki-Miyaura coupling reactions in aqueous media and tolerated various functional groups (even heterocycles) with extremely low catalyst loading. The Royal Society of Chemistry 2010.
- Tu, Tao,Feng, Xike,Wang, Zhixun,Liu, Xiyu
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supporting information; experimental part
p. 10598 - 10600
(2011/01/10)
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- Design of more potent squalene synthase inhibitors with multiple activities
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With the increasing realization that modulating a multiplicity of targets can be an asset in the treatment of multifactorial disorders, we hereby report the synthesis and evaluation of the first compounds in which antioxidant, anti-inflammatory as well as squalene synthase (SQS) inhibitory activities are combined by design, in a series of simple molecules, extending their potential range of activities against the multifactorial disease of atherosclerosis. The activity of the initially synthesized antihyperlipidemic morpholine derivatives (1-6), in which we combined several pharmacophore moieties, was evaluated in vitro (antioxidant, inhibition of SQS and lipoxygenase) and in vivo (anti-dyslipidemic and anti-inflammatory effect). We further compared the in vitro SQS inhibitory action of these derivatives with theoretically derived molecular interactions by performing an in silico docking study using the X-ray crystal structure of human SQS. Based on low energy preferred binding modes, we designed potentially more potent SQS ligands. We proceeded with synthesizing and evaluating these new structures (7-12) in vitro and in vivo, to show that the new derivatives were significantly more active than formerly developed congeners, both as SQS inhibitors (20-70-fold increase in activity) and antioxidants (4-30-fold increase in activity). A significant correlation between experimental activity [Log(1/IC50)] and the corresponding binding free energy (ΔGb) of the docked compounds was shown. These results, taken together, show a promising alternative and novel approach for the design and development of multifunctional antiatherosclerosis agents.
- Kourounakis, Angeliki P.,Matralis, Alexios N.,Nikitakis, Anastasios
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experimental part
p. 7402 - 7412
(2010/12/25)
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- Nickel-catalyzed cross-coupling of aryl methyl ethers with aryl boronic esters
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(Chemical Equation Presented) To C-OMe and go: The title reaction, involving cleavage of a C-OMe bond, is demonstrated for the coupling of aryl methyl ethers on fused aromatic systems, such as naphthalene and phenanthrene, as well as anisoles containing electron-withdrawing groups with a wide range of boronic esters. cod=cycloocta-1,5-diene, Cy=cyclohexyl.
- Tobisu, Mamoru,Shimasaki, Toshiaki,Chatani, Naoto
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experimental part
p. 4866 - 4869
(2009/02/08)
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