- Catalyst shuttling enabled by a thermoresponsive polymeric ligand: Facilitating efficient cross-couplings with continuously recyclable ppm levels of palladium
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A polymeric monophosphine ligand WePhos has been synthesized and complexed with palladium(ii) acetate [Pd(OAc)2] to generate a thermoresponsive pre-catalyst that can shuttle between water and organic phases, with the change being regulated by temperature. The structure of the polymeric ligand was confirmed with matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry and size-exclusion chromatography (SEC) analysis, as well as nuclear magnetic resonance (NMR) measurements. This polymeric metal complex enables highly efficient Pd-catalyzed cross-couplings and tandem reactions using 50 to 500 ppm palladium, and this can facilitate reactions that are tolerant to a broad spectrum of (hetero)aryl substrates and functional groups, as demonstrated with 73 examples with up to 99% isolated yields. Notably, 97% Pd remained in the aqueous phase after 10 runs of catalyst recycling experiments, as determined via inductively coupled plasma-atomic emission spectrometry (ICP-AES) measurements, indicating highly efficient catalyst transfer. Furthermore, a continuous catalyst recycling approach has been successfully developed based on flow chemistry in combination with the catalyst shuttling behavior, allowing Suzuki-Miyaura couplings to be conducted at gram-scales with as little as 10 ppm Pd loading. Given the significance of transition-metal catalyzed cross-coupling and increasing interest in sustainable chemistry, this work is an important step towards the development of a responsive catalyst, in addition to having high activity, by tuning the structures of the ligands using polymer science.
- Wang, Erfei,Chen, Mao
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p. 8331 - 8337
(2019/09/30)
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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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- [2,2′-bipyridin]-6(1 H)-one, a Truly Cooperating Ligand in the Palladium-Mediated C-H Activation Step: Experimental Evidence in the Direct C-3 Arylation of Pyridine
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The ligand [2,2′-bipyridin]-6(1H)-one (bipy-6-OH) has a strong accelerating effect on the Pd-catalyzed direct arylation of pyridine or arenes. The isolation of relevant intermediates and the study of their decomposition unequivocally show that the deprotonated coordinated ligand acts as a base and assists the cleavage of the C-H bond. Mechanistic work indicates that the direct arylation of pyridine with this ligand occurs through a Pd(0)/Pd(II) cycle. Because of this dual ligand-intramolecular base role, there is no need for an available coordination site on the metal for an external base, a difficulty encountered when chelating ligands are used in coupling reactions that involve a C-H cleavage step.
- Salamanca, Vanesa,Toledo, Alberto,Albéniz, Ana C.
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supporting information
p. 17851 - 17856
(2019/01/04)
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- Electron-Catalyzed Cross-Coupling of Arylboron Compounds with Aryl Iodides
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Arylboroxines in combination with zinc chloride and potassium tert-butoxide were found to undergo the electron-catalyzed cross-coupling with aryl iodides to give the corresponding biaryls without the aid of transition-metal catalysis.
- Okura, Keisho,Teranishi, Tsuyoshi,Yoshida, Yuto,Shirakawa, Eiji
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supporting information
p. 7186 - 7190
(2018/06/15)
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- Method of manufacturing hydroxybiphenyls
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PROBLEM TO BE SOLVED: To provide a convenient production method of biphenyls which become the raw materials of medicines, pesticides and functional materials. SOLUTION: In the presence of a palladium catalyst and an alkali metal carboxylate, a 2,2'-bi(1,3,2-benzodioxaborole) derivative represented by general formula (1) (in formula, R1represents a hydrogen atom or a 1-4C alkyl group) and a benzene derivative A are made to react with each other, next, in the presence of an alkali metal phosphate or an alkali metal carbonate, a benzene derivative B is made to react therewith, and biphenyls represented by general formula (4) (in formula, each of R2and R3represents a hydrogen atom, a halogen atom, or the like, and each of n and m represents an integer of 1 to 4) are produced. COPYRIGHT: (C)2013,JPOandINPIT
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Paragraph 0071-0072
(2020/11/19)
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- Highly functionalized biaryls via Suzuki-Miyaura cross-coupling catalyzed by Pd@MOF under batch and continuous flow regimes
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A diverse set of more than 40 highly functionalized biaryls was synthesized successfully through the Suzuki-Miyaura cross-coupling reaction catalyzed by Pd nanoparticles supported in a functionalized mesoporous MOF (8 wt% Pd@MIL-101(Cr)-NH2). This could be achieved under some of the mildest conditions reported to date and a strong control over the leaching of metallic species could be maintained, despite the presence of diverse functional groups and/or several heteroatoms. Some of the targeted molecules are important intermediates in the synthesis of pharmaceuticals and we clearly exemplify the versatility of this catalytic system, which affords better yields than currently existing commercial procedures. Most importantly, Pd@MIL-101-NH2 was packed in a micro-flow reactor, which represents the first report of metallic nanoparticles supported on MOFs employed in flow chemistry for catalytic applications. A small library of 11 isolated compounds was created in a continuous experiment without replacing the catalyst, demonstrating the potential of the catalyst for large-scale applications.
- Pascanu, Vlad,Hansen, Peter R.,Bermejo G?3mez, Antonio,Ayats, Carles,Platero-Prats, Ana E.,Johansson, Magnus J.,Peric??s, Miquel ??.,Mart??n-Matute, Bel??n
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p. 123 - 130
(2015/02/19)
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- Single-electron-transfer-induced coupling of arylzinc reagents with aryl and alkenyl halides
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Arylzinc reagents, prepared from aryl halides/zinc powder or aryl Grignard reagents/zinc chloride, were found to undergo coupling with aryl and alkenyl halides without the aid of transition-metal catalysis to give biaryls and styrene derivatives, respectively. In this context, we have already reported the corresponding reaction using aryl Grignard reagents instead of arylzinc reagents. Compared with the Grignard cross-coupling, the present reaction features high functional-group tolerance, whereby electrophilic groups such as alkoxycarbonyl and cyano groups are compatible as substituents on both the arylzinc reagents and the aryl halides. Aryl halides receive a single electron and thereby become activated as the corresponding anion radicals, which react with arylzinc reagents, thus leading to the cross-coupling products. Arylzinc reagents were found to undergo coupling with aryl and alkenyl halides to give biaryl and styrene derivatives, respectively. The cross-coupling, which features high functional-group tolerance, proceeds through a single-electron-transfer mechanism and thus does not require the aid of transition-metal catalysis.
- Shirakawa, Eiji,Tamakuni, Fumiko,Kusano, Eugene,Uchiyama, Nanase,Konagaya, Wataru,Watabe, Ryo,Hayashi, Tamio
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p. 521 - 525
(2014/01/23)
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- Mono- and dinuclear pincer nickel catalyzed activation and transformation of C-Cl, C-N, and C-O bonds
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Condensation of 2-NH2C6H4P(Et)Ph (2) with pyrrole-2-carboxaldehyde generated 2-(C4H4N-2′-CH - N)C6H4P(Et)Ph (3). Treatment of 3 with NaH and followed by (DME)NiX2 (X = Cl, Br) afforded mononuclear pincer nickel complexes [Ni{2-(C4H3N-2′-CH - N)C6H4P(Et)Ph}X] (4a, X = Cl; 4b, X = Br). Reaction of [2-NH2C6H4P(Ph)]2(CH2)n (5a, n = 3; 5b, n = 4) with pyrrole-2-carboxaldehyde or 5-tert-butyl-1H-pyrrole-2-carbaldehyde formed [2-(C4H4N-2′-CH - N)C6H4P(Ph)]2(CH2)n (6a, n = 3; 6b, n = 4) and [2-(5′-tBuC4H3N-2′-CH - N)C6H4P(Ph)]2(CH2)4 (6c). Respective treatment of 6a-c with NaH followed by (DME)NiX2 (X = Cl, Br) gave the dinuclear nickel complexes [Ni{2-(5′-RC4H2N-2′-CH - N)C6H4P(Ph)}X]2(CH2)n (7a, R = H, X = Cl, n = 3; 7b, R = H, X = Cl, n = 4; 7c, R = H, X = Br, n = 4; 7d, R = tBu, X = Cl, n = 4). Catalysis of the complexes for the activation and transformation of C-Cl, C-N, and C-O bonds was evaluated. Complex 7c exhibited excellent catalytic activity in the cross-coupling of aryl chlorides or aryltrimethylammonium iodides with arylzinc reagents as well as of aryl sulfamates with aryl Grignard reagents. The dinuclear nickel complexes 7b-d showed higher catalytic activity than the mononuclear complexes in each type of reaction.
- Yang, Xia,Wang, Zhong-Xia
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p. 5863 - 5873
(2015/01/09)
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- P,N,N-Pincer nickel-catalyzed cross-coupling of aryl fluorides and chlorides
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P,N,N-Pincer nickel complexes [Ni(Cl){N(2-R2PC6H 4)(2′-Me2NC6H4)}] (R = Ph, 3a; R = Pri, 3b; R = Cy, 3c) were synthesized and their catalysis toward the Kumada or Negishi cross-coupling reaction of aryl fluorides and chlorides was evaluated. Complex 3a effectively catalyzes the cross-coupling of (hetero)aryl fluorides with aryl Grignard reagents at room temperature. Complex 3a also catalyzes the cross-coupling of (hetero)aryl chlorides and arylzinc reagents at 80 °C with low catalyst loadings and good functional group compatibility. the Partner Organisations 2014.
- Wu, Dan,Wang, Zhong-Xia
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p. 6414 - 6424
(2014/08/18)
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- Palladium-catalyzed cross-coupling reaction of aryl(trialkyl)silanes with aryl nitriles
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Using highly stable, readily accessible, and recyclable 2-(2-hydroxyprop-2-yl)cyclohexyl-substituted arylsilanes activated by a mild phosphate base, palladium-catalyzed silicon-based aryl-aryl cross-coupling reaction proceeds for the first time with aryl nitriles in a highly chemoselective manner.
- Tang, Shi,Li, Shu-Hua,Yan, Wen-Bin
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p. 6743 - 6746
(2013/01/15)
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- Nickel complexes supported by quinoline-based ligands: Synthesis, characterization and catalysis in the cross-coupling of arylzinc reagents and aryl chlorides or aryltrimethylammonium salts
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Lithium and nickel complexes bearing quinoline-based ligands have been synthesized and characterized. Reaction of 8-azidoquinoline with Ph 2PNHR (R = p-MeC6H4, But) affords N-(8-quinolyl)iminophosphoranes RNHP(Ph2)N(8-C9H 6N) (1a, R = p-MeC6H4; 1b, R = But. C9H6N = quinolyl)). Reaction of 1a with (DME)NiCl 2 generates a nickel complex [NiCl2{N(8-C 9H6N)P(Ph2)NH(p-MeC6H4)}] (2a). Treatment of 1b with (DME)NiCl2 and following with NaH produces [NiCl{(1,2-C6H4)P(Ph)(NHBut)N(8-C 9H6N)}] (4). Complex 4 was also obtained by reaction of (DME)NiCl2 with [Li{(1,2-C6H4)P(Ph)(NHBu t)N(8-C9H6N)}] (5) prepared through lithiation of 1b. Reaction of 2-PyCH2P(Ph2)N(8-C9H 6N) (6, Py = pyridyl) and PhNC(Ph)CH2P(Ph 2)N(8-C9H6N) (8), respectively, with (DME)NiCl2 yields two five-coordinate N,N,N-chelate nickel complexes, [NiCl2{2-PyCH2P(Ph2)N(8-C9H 6N)}] (7) and [NiCl2{PhNC(Ph)CH2P(Ph 2)N(8-C9H6N)}] (9). Similar reaction between Ph2PCH2P(Ph2)N(8-C9H6N) (10) and (DME)NiCl2 results in five-coordinate N,N,P-chelate nickel complex [NiCl2{Ph2PCH2P(Ph2)N(8- C9H6N)}] (11). Treatment of [(8-C9H 6N)NP(Ph2)]2CH2 (12) [prepared from (Ph2P)2CH2 and 2 equiv. of 8-azidoquinoline] with LiBun and (DME)NiCl2 successively affords [NiCl{(8-C9H6N)NP(Ph2)}2CH] (13). The new compounds were characterized by 1H, 13C and 31P NMR spectroscopy (for the diamagnetic compounds), IR spectroscopy (for the nickel complexes) and elemental analysis. Complexes 2a, 4, 7, 9, 11 and 13 were also characterized by single-crystal X-ray diffraction techniques. The nickel complexes were evaluated for the catalysis in the cross-coupling reactions of arylzinc reagents with aryl chlorides and aryltrimethylammonium salts. Complex 7 exhibits the highest activity among the complexes in catalyzing the reactions of arylzinc reagents with either aryl chlorides or aryltrimethylammonium bromides.
- Zhang, Qiang,Zhang, Xue-Qi,Wang, Zhong-Xia
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p. 10453 - 10464,12
(2020/08/31)
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- Direct Pd-catalyzed cross-coupling of functionalized organoaluminum reagents
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A handsome couple: Through the use of the simple Pd catalyst [Pd(tmpp) 2Cl2] (tmpp=tris(2,4,6-trimethoxyphenyl)phosphine) and THF/DMF as solvent, various aryl-, heteroaryl-, benzyl- and alkylaluminum reagents can be readily cross-coupled with aryl or heteroaryl iodides, bromides, and nonaflates, and in special cases even with chlorides and triflates. This cross-coupling tolerates free NH2 groups, aldehydes, ketones, esters, and nitro functions. Copyright
- Groll, Klaus,Bluemke, Tobias D.,Unsinn, Andreas,Haas, Diana,Knochel, Paul
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supporting information
p. 11157 - 11161,5
(2012/12/12)
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- Nickel-catalyzed cross-coupling of arene-or heteroarenecarbonitriles with aryl-or heteroarylmanganese reagents through C-CN bond activation
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The nickel-catalyzed cross-coupling reaction of arene- or heteroarenecarbonitriles with aryl- or heteroarylmanganese reagents via C-CN bond activation has been developed. Both electron-rich and electron-deficient nitriles can be employed as the electrophilic substrates. The reaction tolerates a range of functional groups and aromatic heterocycles. Copyright
- Liu, Ning,Wang, Zhong-Xia
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supporting information; experimental part
p. 1641 - 1645
(2012/07/31)
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- Cross-coupling of aryltrimethylammonium iodides with arylzinc reagents catalyzed by amido pincer nickel complexes
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The cross-coupling reaction of aryltrimethylammonium iodides with aryl- or heteroarylzinc chlorides catalyzed by amido pincer nickel complexes was performed. The reaction requires low catalyst loading and displays broad substrate scope.
- Zhang, Xue-Qi,Wang, Zhong-Xia
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experimental part
p. 3658 - 3663
(2012/05/20)
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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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- Room-temperature palladium-catalyzed Negishi-type coupling: A combined experimental and theoretical study
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An air-stable, bulky electron-accepting phosphine ligand (phosphabarrelene) allows the easy reduction of a PdII precursor to a Pd0 complex, highly active in room-temperature Negishi-type cross-coupling. DFT calculations show that the use of the electron-accepting ligand favors both transmetalation (TM) and reductive-elimination (RE) processes (see scheme; OA=oxidative addition).
- Ribagnac, Philippe,Blug, Matthias,Villa-Uribe, Jose,Le Goff, Xavier-Frederic,Gosmini, Corinne,Mezailles, Nicolas
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experimental part
p. 14389 - 14393
(2012/02/06)
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- Nickel-catalyzed cross-coupling of aryltrimethylammonium iodides with organozinc reagents
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Broad scope and good tolerance: An efficient cross-coupling of aryltrimethylammonium iodide salts with aryl-, methyl-, and benzylzinc chlorides catalyzed by [Ni(PCy3)2Cl2] has been achieved (see scheme). The reaction involves cleavage of the C-N bond and displays broad substrate scope and good functional group tolerance. NMP=N-methylpyrrolidine. Copyright
- Xie, Lan-Gui,Wang, Zhong-Xia
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supporting information; experimental part
p. 4901 - 4904
(2011/06/22)
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- Dicarboxylic Acid Derivatives and their Use
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The present application relates to novel dicarboxylic acid derivatives, process for their preparation, their use for the treatment and/or prophylaxis of diseases, and their use for producing medicaments for the treatment and/or prophylaxis of diseases, es
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Page/Page column 18
(2010/03/02)
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- Heterocyclic compounds with carboxyl isostere groups and their use for the treatment of cardiovascular diseases
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The present application relates to novel heterocyclic compounds, processes for their preparation, their use for the treatment and/or prophylaxis of diseases, and their use for producing medicaments for the treatment and/or prophylaxis of diseases, especia
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Page/Page column 38
(2009/09/25)
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- Difluorophenol Derivatives and Their Use
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The present application relates to novel difluorophenol derivatives, processes for their preparation, their use for the treatment and/or prophylaxis of diseases, and their use for producing medicaments for the treatment and/or prophylaxis of diseases, especially for the treatment and/or prevention of cardiovascular disorders.
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Page/Page column 24
(2009/12/05)
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- Tetrazole Derivatives and Their Use for the Treatment of Cardiovascular Diseases
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The present application relates to novel tetrazole derivatives, processes for their preparation, their use for the treatment and/or prophylaxis of diseases, and their use for producing medicaments for the treatment and/or prophylaxis of diseases, especial
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Page/Page column 30
(2009/09/07)
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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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- Convenient preparation of polyfunctional aryl magnesium reagents by a direct magnesium insertion in the presence of LiCl
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(Chemical Equation Presented) In the footsteps of Victor Grignard: The simple LiCl-mediated insertion of magnesium into aryl chlorides and bromides at moderate temperatures leads to functionalized organomagnesium reagents (see scheme). An unprecedented range of functional groups may be present in the substrates (e.g. CN, CO2R, OTs, OBoc; Ts=p-toluenesulfonyl, Boc=tert-butylcarbonyloxy).
- Piller, Fabian M.,Appukkuttan, Prasad,Gavryushin, Andrei,Helm, Matthew,Knochel, Paul
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supporting information; experimental part
p. 6802 - 6806
(2009/04/06)
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- Efficient cobalt-catalyzed formation of unsymmetrical biaryl compounds and its application in the synthesis of a sartan intermediate
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(Chemical Equation Presented) No prior preparation of the organometallic reagent is required in a cobalt-catalyzed coupling of two different aryl halides under mild conditions (see scheme). A broad spectrum of valuable biaryl compounds can be prepared in this way. Not only may a variety of reactive substituents be present, but heteroaryl halides and aryl triflates are also suitable substrates. DMF = N,N-dimethylformamide, FG = functional group.
- Amatore, Muriel,Gosmini, Corinne
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supporting information; experimental part
p. 2089 - 2092
(2009/02/06)
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- Palladium-catalyzed cross-coupling reactions of substituted aryl(dimethyl)silanols
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Cesium carbonate and cesium hydroxide monohydrate are effective activators for the palladium-catalyzed cross-coupling of aryl(dimethyl)silanols with substituted aryl halides. Extensive optimization studies led to the identification of key variables (solvent, catalyst, additive, and hydration level) that influence the rate and selectivity of the process. Manipulation of these factors provides an effective coupling method of wide scope and generality. Electron-rich aryl(dimethyl)silanols undergo cross-coupling with aryl iodides and aryl bromides in high yields and high selectivity for the desired cross-coupling products. Alternatively, high yields of cross-coupling products could be obtained with electron-poor or ortho-substituted aryl(dimethyl)silanols when activated with cesium hydroxide monohydrate.
- Denmark, Scott E.,Ober, Michael H.
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p. 1703 - 1714
(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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